WorldWideScience

Sample records for supercritical methanol electronic

  1. Pulse radiolysis study on temperature and pressure dependence of the yield of solvated electron in methanol from room temperature to supercritical condition

    International Nuclear Information System (INIS)

    Han, Zhenhui; He, Hui; Lin, Mingzhang; Muroya, Yusa; Katsumura, Yosuke

    2012-09-01

    A new concept of nuclear reactor, supercritical water-cooled reactor (SCWR), has been proposed, which is based on the success of the use of supercritical water (SCW) in fossil fuel power plants for more than three decades. This new concept reactor has advantages of higher thermal conversion efficiency, simplicity in structure, safety, etc, and it has been selected as one of the reactor concepts for the next generation nuclear reactor systems. In these reactors, the same as in boiling water reactors (BWR) and pressurized water reactors (PWR), water is used not only as a coolant but also as a moderator. It is very important to understand the behavior of the radiolysis products of water under the supercritical condition, since the water is exposed to a strong radiation field under very high temperature condition. Usually, in order to predict the concentrations of water decomposition products with carrying out some kinds of computer simulations, knowledge of the temperature and/or pressure dependent G-values (denoting the experimentally measured radiolytic yields) as well as of the rate constants of a set of reactions becomes very important. Therefore, in recent years, two groups from Argonne National Laboratory and The University of Tokyo, simultaneously conducted two projects aimed at obtaining basic data on radiolysis of SCW. However, it is still lack of reliable radiolytic yields of water decomposition products in very high temperature region. As we known, the properties of solvated electrons in polar liquid are very helpful for our understanding how they play a central role in many processes, such as solvation and reducing reactions. The solvated electron can also be used as a probe to determine the dynamic nature of the polar liquid systems. Comparing to water, the primary alcohols have much milder critical points, for example, for water and methanol, the critical temperature and pressure are 374 deg. C and 22.1 MPa and 239.5 deg. C and 8.1 MPa, respectively

  2. Thermal stability of biodiesel in supercritical methanol

    Energy Technology Data Exchange (ETDEWEB)

    Hiroaki Imahara; Eiji Minami; Shusaku Hari; Shiro Saka [Kyoto University, Kyoto (Japan). Department of Socio-Environmental Energy Science

    2008-01-15

    Non-catalytic biodiesel production technologies from oils/fats in plants and animals have been developed in our laboratory employing supercritical methanol. Due to conditions in high temperature and high pressure of the supercritical fluid, thermal stability of fatty acid methyl esters and actual biodiesel prepared from various plant oils was studied in supercritical methanol over a range of its condition between 270{sup o}C/17 MPa and 380{sup o}C/56 MPa. In addition, the effect of thermal degradation on cold flow properties was studied. As a result, it was found that all fatty acid methyl esters including poly-unsaturated ones were stable at 270{sup o}C/17 MPa, but at 350{sup o}C/43 MPa, they were partly decomposed to reduce the yield with isomerization from cis-type to trans-type. These behaviors were also observed for actual biodiesel prepared from linseed oil, safflower oil, which are high in poly-unsaturated fatty acids. Cold flow properties of actual biodiesel, however, remained almost unchanged after supercritical methanol exposure at 270{sup o}C/17 MPa and 350{sup o}C/43 MPa. For the latter condition, however, poly-unsaturated fatty acids were sacrificed to be decomposed and reduced in yield. From these results, it was clarified that reaction temperature in supercritical methanol process should be lower than 300{sup o}C, preferably 270{sup o}C with a supercritical pressure higher than 8.09 MPa, in terms of thermal stabilization for high-quality biodiesel production. 9 refs., 3 figs., 4 tabs.

  3. Oxidation stability of biodiesel fuel as prepared by supercritical methanol

    Energy Technology Data Exchange (ETDEWEB)

    Jiayu Xin; Hiroaki Imahara; Shiro Saka [Kyoto University, Kyoto (Japan). Department of Socio-Environmental Energy Science, Graduate School of Energy Science

    2008-08-15

    A non-catalytic supercritical methanol method is an attractive process to convert various oils/fats efficiently into biodiesel. To evaluate oxidation stability of biodiesel, biodiesel produced by alkali-catalyzed method was exposed to supercritical methanol at several temperatures for 30 min. As a result, it was found that the tocopherol in biodiesel is not stable at a temperature higher than 300{sup o}C. After the supercritical methanol treatment, hydroperoxides were greatly reduced for biodiesel with initially high in peroxide value, while the tocopherol slightly decreased in its content. As a result, the biodiesel prepared by the supercritical methanol method was enhanced for oxidation stability when compared with that prepared by alkali-catalyzed method from waste oil. Therefore, supercritical methanol method is useful especially for oils/fats having higher peroxide values. 32 refs., 8 figs., 3 tabs.

  4. Experimental study on methanol recovery through flashing vaporation in continuous production of biodiesel via supercritical methanol

    International Nuclear Information System (INIS)

    Wang Cunwen; Chen Wen; Wang Weiguo; Wu Yuanxin; Chi Ruan; Tang Zhengjiao

    2011-01-01

    To improve the oil conversion, high methanol/oil molar ratio is required in the continuous production of biodiesel via supercritical methanol transesterification in tubular reactor. And thus the subsequent excess methanol recovery needs high energy consumption. Based on the feature of high temperature and high pressure in supercritical methanol transesterification, excess methanol recovery in reaction system by flashing vaporation is conducted and the effect of reaction temperature, reaction pressure and flashing pressure on methanol recovery and methanol concentration in gas phase is discussed in detail in this article. Results show that at the reaction pressure of 9-15 MPa and the reaction temperature of 240-300 o C, flashing pressure has significant influence on methanol recovery and methanol content in gas phase, which can be effectively improved by reducing flashing pressure. At the same time, reaction temperature and reaction pressure also have an important effect on methanol recovery and methanol content in gas phase. At volume flow of biodiesel and methanol 1:2, tubular reactor pressure 15 MPa, tubular reactor temperature 300 o C and the flashing pressure 0.4 MPa, methanol recovery is more than 85% and methanol concentration of gas phase (mass fraction) is close to 99% after adiabatic braising; therefore, the condensate liquid of gas phase can be injected directly into methanol feedstock tank to be recycled. Research abstracts: Biodiesel is an important alternative energy, and supercritical methanol transesterification is a new and green technology to prepare biodiesel with some obvious advantages. But it also exists some problems: high reaction temperature, high reaction pressure and large molar ratio of methanol/oil will cause large energy consumption which restricts supercritical methanol for the industrial application of biodiesel. So a set of tubular reactor-coupled flashing apparatus is established for continuous preparing biodiesel in supercritical

  5. Biodiesel Production from Acidified Oils via Supercritical Methanol

    Directory of Open Access Journals (Sweden)

    Jianxin Li

    2011-12-01

    Full Text Available In biodiesel production, the vegetable oil used as raw material for transesterification should be free of water and free fatty acids (FFAs, which may consume catalyst and reduce catalyst efficiency. In this work biodiesel was prepared from acidified oils (AO through a supercritical methanol route, in which the esterification of FFAs and transesterification of glyceride with methanol occurred simultaneously. The effects of the mass ratio of methanol to AO, the operation temperature as well as the water content on the FFAs conversion and glycerol yield were investigated. The results indicated that the FFAs conversion for esterification under the condition of 1:1 methanol/oil ratio, 310 °C and 15 min reaction time reached 98.7%, and the glycerol yield for transesterification under 0.25:1 methanol/oil ratio, 290 °C and 20 min reaction time reached 63.5% respectively.

  6. Biodiesel from sunflower oil in supercritical methanol with calcium oxide

    International Nuclear Information System (INIS)

    Demirbas, Ayhan

    2007-01-01

    In this study, sunflower seed oil was subjected to the transesterification reaction with calcium oxide (CaO) in supercritical methanol for obtaining biodiesel. Methanol is used most frequently as the alcohol in the transesterification process. Calcium oxide (CaO) can considerably improve the transesterification reaction of sunflower seed oil in supercritical methanol. The variables affecting the methyl ester yield during the transesterification reaction, such as the catalyst content, reaction temperature and the molar ratio of soybean oil to alcohol, were investigated and compared with those of non-catalyst runs. The catalytic transesterification ability of CaO is quite weak under ambient temperature. At a temperature of 335 K, the yield of methyl ester is only about 5% in 3 h. When CaO was added from 1.0% to 3.0%, the transesterification speed increased evidently, while when the catalyst content was further enhanced to 5%, the yield of methyl ester slowly reached to a plateau. It was observed that increasing the reaction temperature had a favorable influence on the methyl ester yield. In addition, for molar ratios ranging from 1 to 41, as the higher molar ratios of methanol to oil were charged, the greater transesterification speed was obtained. When the temperature was increased to 525 K, the transesterification reaction was essentially completed within 6 min with 3 wt% CaO and 41:1 methanol/oil molar ratio

  7. TRANSESTERIFICATION OF VEGETABLES OIL USING SUBAND SUPERCRITICAL METHANOL

    Directory of Open Access Journals (Sweden)

    Nyoman Puspa Asri

    2012-11-01

    Full Text Available A benign process, non catalytic transesterification in sub and supercritical methanol method was usedto prepare biodiesel from vegetables oil. The experiment was carried out in batch type reactor (8.8 mlcapacity, stainless steel, AKICO, JAPAN by changing the reaction condition such as reactiontemperature (from 210°C in subcritical condition to 290°C in supercritical state with of 20°Cinterval, molar ratio oil to methanol (1:12-1:42 and time of reaction (10-90 min. The fatty acidmethyl esters (FAMEs content was analyzed by gas chromatography-flame ionization detector (GCFID.Such analysis can be used to determine the biodiesel yield of the transesterification. The resultsshowed that the yield of biodiesel increases gradually with the increasing of reaction time atsubcritical state (210-230oC. However, it was drastically increased at the supercritical state (270-290oC. Similarly, the yield of biodiesel sharply increased with increasing the ratio molar of soy oilmethanolup to 1:24. The maximum yield 86 and 88% were achieved at 290oC, 90 min of reaction timeand molar ratio of oil to methanol 1:24, for soybean oil and palm oil, respectively.Proses transesterifikasi non katalitik dengan metanol sub dan superkritis,merupakan proses yang ramah lingkungan digunakan untuk pembuatan biodiesel dari minyak nabati.Percobaan dilakukan dalam sebuah reaktor batch (kapasitas 8,8 ml, stainless steel, AKICO, JAPAN,dengan variabel kondisi reaksi seperti temperatur reaksi (dari kondisi subkritis 210°C-kondisisuperkritis 290°C dengan interval 20°C, rasio molar minyak-metanol (1:12-1:42 dan waktu reaksi(10-90 menit. Kandungan metil ester asam lemak (FAME dianalisis dengan kromatografi gasdengan detektor FID (GC-FID. Hasil Analisis tersebut dapat digunakan untuk menentukan yieldbiodiesel dari proses transesterifikasi. Hasil penelitian menunjukkan bahwa yield biodiesel meningkatsecara perlahan dengan meningkatnya waktu reaksi pada keadaan subkritis (210-230oC. Namun

  8. Production of FAME by palm oil transesterification via supercritical methanol technology

    International Nuclear Information System (INIS)

    Tan, Kok Tat; Lee, Keat Teong; Mohamed, Abdul Rahman

    2009-01-01

    The present study employed non-catalytic supercritical methanol technology to produce biodiesel from palm oil. The research was carried out in a batch-type tube reactor and heated beyond supercritical temperature and pressure of methanol, which are at 239 o C and 8.1 MPa respectively. The effects of temperature, reaction time and molar ratio of methanol to palm oil on the yield of fatty acid methyl esters (FAME) or biodiesel were investigated. The results obtained showed that non-catalytic supercritical methanol technology only required a mere 20 min reaction time to produce more than 70% yield of FAME. Compared to conventional catalytic methods, which required at least 1 h reaction time to obtain similar yield, supercritical methanol technology has been shown to be superior in terms of time and energy consumption. Apart from the shorter reaction time, it was found that separation and purification of the products were simpler since no catalyst is involved in the process. Hence, formation of side products such as soap in catalytic reactions does not occur in the supercritical methanol method.

  9. Biodiesel from waste cooking oil via base-catalytic and supercritical methanol transesterification

    International Nuclear Information System (INIS)

    Demirbas, Ayhan

    2009-01-01

    In this study, waste cooking oil has subjected to transesterification reaction by potassium hydroxide (KOH) catalytic and supercritical methanol methods obtaining for biodiesel. In catalyzed methods, the presence of water has negative effects on the yields of methyl esters. In the catalytic transesterification free fatty acids and water always produce negative effects since the presence of free fatty acids and water causes soap formation, consumes catalyst, and reduces catalyst effectiveness. Free fatty acids in the waste cooking oil are transesterified simultaneously in supercritical methanol method. Since waste cooking oil contains water and free fatty acids, supercritical transesterification offers great advantage to eliminate the pre-treatment and operating costs. The effects of methanol/waste cooking oils ratio, potassium hydroxide concentration and temperature on the biodiesel conversion were investigated

  10. Supercritical methanol drying as a convenient route to phenolic-furfural aerogels

    Energy Technology Data Exchange (ETDEWEB)

    Albert, Donald F.; Bruno, Joseph W. [Department of Chemistry, Wesleyan University, 06459 Middletown, CT (United States); Andrews, Greg R.; Mendenhall, Robert S. [American Aerogel Corporation, 1000 Corporate Row, 06416 Cromwell, CT (United States)

    2001-12-01

    Organic aerogels are prepared by the acid catalyzed cross-linking of phenolic-furfural (PF) precursors in methanol solution, and the solvent is subsequently removed at high temperature as the supercritical fluid. The resulting aerogel is a brown opaque solid and has been prepared as 30 ml cylindrical monoliths exhibiting little or no shrinkage during formation. These solids, which are routinely available with a density as low as ca. 125mg/cm{sup 3}, have been characterized by chemical methods (infrared spectroscopy and CP-MAS 13C NMR spectrometry) and physical techniques (Brunauer-Emmet-Teller surface area, transmission and scanning electron microscopy). In addition, thermal conductivities have been determined, and show that the PF aerogels are excellent thermal insulators. These studies establish that the materials described herein exhibit chemical and physical properties very similar to those seen for organic aerogels prepared with low temperature processing techniques. The current method constitutes a convenient and rapid route to organic aerogels.

  11. Biodiesel production from Spirulina microalgae feedstock using direct transesterification near supercritical methanol condition.

    Science.gov (United States)

    Mohamadzadeh Shirazi, Hamed; Karimi-Sabet, Javad; Ghotbi, Cyrus

    2017-09-01

    Microalgae as a candidate for production of biodiesel, possesses a hard cell wall that prevents intracellular lipids leaving out from the cells. Direct or in situ supercritical transesterification has the potential for destruction of microalgae hard cell wall and conversion of extracted lipids to biodiesel that consequently reduces the total energy consumption. Response surface methodology combined with central composite design was applied to investigate process parameters including: Temperature, Time, Methanol-to-dry algae, Hexane-to-dry algae, and Moisture content. Thirty-two experiments were designed and performed in a batch reactor, and biodiesel efficiency between 0.44% and 99.32% was obtained. According to fatty acid methyl ester yields, a quadratic experimental model was adjusted and the significance of parameters was evaluated using analysis of variance (ANOVA). Effects of single and interaction parameters were also interpreted. In addition, the effect of supercritical process on the ultrastructure of microalgae cell wall using scanning electron spectrometry (SEM) was surveyed. Copyright © 2017 Elsevier Ltd. All rights reserved.

  12. Esterification kinetics of free fatty acids with supercritical methanol for biodiesel production

    International Nuclear Information System (INIS)

    Alenezi, R.; Leeke, G.A.; Winterbottom, J.M.; Santos, R.C.D.; Khan, A.R.

    2010-01-01

    Non-catalytic esterification of Free Fatty Acids (FFA) with supercritical methanol was studied under reaction conditions of (250-320 deg. C) at 10 MPa. A detailed experimental programme was implemented to investigate the influence of temperature, stirring rate and the molar ratio of methanol to FFA in the feed in a batch-type reaction vessel. The esterification products of FFA with supercritical methanol are Fatty Acids Methyl Esters (FAME; biodiesel) and water. The yield of FAME was found to increase with an increase in temperature, and with an increase in the molar ratio of methanol to FFA. At >850 rpm the yield of FAME was not affected by stirring rate. The rate constants and energy of activation have been numerically evaluated by solving an ordinary differential equation that describes the reaction kinetics. The proposed kinetic model shows a reversible second order reaction and represents all the experimental data satisfactorily, providing deeper insight into the kinetics of the reaction.

  13. A closer study of methanol adsorption and its impact on solute retentions in supercritical fluid chromatography.

    Science.gov (United States)

    Glenne, Emelie; Öhlén, Kristina; Leek, Hanna; Klarqvist, Magnus; Samuelsson, Jörgen; Fornstedt, Torgny

    2016-04-15

    Surface excess adsorption isotherms of methanol on a diol silica adsorbent were measured in supercritical fluid chromatography (SFC) using a mixture of methanol and carbon dioxide as mobile phase. The tracer pulse method was used with deuterium labeled methanol as solute and the tracer peaks were detected using APCI-MS over the whole composition range from neat carbon dioxide to neat methanol. The results indicate that a monolayer (4Å) of methanol is formed on the stationary phase. Moreover, the importance of using the set or the actual methanol fractions and volumetric flows in SFC was investigated by measuring the mass flow respective pressure and by calculations of the actual volume fraction of methanol. The result revealed a significant difference between the value set and the actually delivered volumetric methanol flow rate, especially at low modifier fractions. If relying only on the set methanol fraction in the calculations, the methanol layer thickness should in this system be highly overestimated. Finally, retention times for a set of solutes were measured and related to the findings summarized above concerning methanol adsorption. A strongly non-linear relationship between the logarithms of the retention factors and the modifier fraction in the mobile phase was revealed, prior to the established monolayer. At modifier fractions above that required for establishment of the methanol monolayer, this relationship turns linear which explains why the solute retention factors are less sensitive to changes in modifier content in this region. Copyright © 2016 Elsevier B.V. All rights reserved.

  14. Transesterification of rapeseed and palm oils in supercritical methanol and ethanol

    International Nuclear Information System (INIS)

    Biktashev, Sh.A.; Usmanov, R.A.; Gabitov, R.R.; Gazizov, R.A.; Gumerov, F.M.; Gabitov, F.R.; Abdulagatov, I.M.; Yarullin, R.S.; Yakushev, I.A.

    2011-01-01

    The results of the rapeseed and palm oils transesterification with supercritical methanol and ethanol were presented. The studies were performed using the experimental setups which are working in batch and continuous regimes. The effect of reaction conditions (temperature, pressure, oil to alcohol ratio, reaction time) on the biodiesel production (conversion yield) was studied. Also the effect of preliminary ultrasonic treatment (ultrasonic irradiation, emulsification of immiscible oil and alcohol mixture) of the initial reagents (emulsion preparation) on the stage before transesterification reaction conduction on the conversion yield was studied. We found that the preliminary ultrasonic treatment of the initial reagents increases considerably the conversion yield. Optimal technological conditions were determined to be as follows: pressure within 20-30 MPa, temperature within 573-623 K. The optimal values of the oil to alcohol ratio strongly depend on preliminary treatment of the reaction mixture. The study showed that the conversion yield at the same temperature with 96 wt.% of ethanol is higher than with 100 wt.% of methanol. -- Highlights: → The results of the rapeseed and palm oils transesterification with supercritical methanol and ethanol were presented. → The effect of reaction conditions (temperature, pressure, oil to alcohol ratio, reaction time) on the biodiesel production (conversion yield) was studied. → Transesterification of vegetable oil with supercritical alcohols. → Effect of temperature and pressure on conversion yield. → Preliminary ultrasonic treatment of the vegetable oil+methanol mixture.

  15. One-pot reduction of 5-hydroxymethylfurfural via hydrogen transfer from supercritical methanol

    DEFF Research Database (Denmark)

    Hansen, Thomas Søndergaard; Barta, Katalin; Anastas, Paul T.

    2012-01-01

    Catalytic conversion of HMF to valuable chemicals was achieved over a Cu-doped porous metal oxide in supercritical methanol. The hydrotalcite catalyst precursor is prepared following simple synthetic procedures, using inexpensive and earth-abundant starting materials in aqueous solutions. The hyd......Catalytic conversion of HMF to valuable chemicals was achieved over a Cu-doped porous metal oxide in supercritical methanol. The hydrotalcite catalyst precursor is prepared following simple synthetic procedures, using inexpensive and earth-abundant starting materials in aqueous solutions....... The hydrogen equivalents needed for the reductive deoxygenation of HMF originate from the solvent itself upon its reforming. Dimethylfuran, dimethyltetrahydrofuran and 2-hexanol were obtained in good yields. At milder reaction temperatures, a combined yield (DMF + DMTHF) of 58% was achieved. Notably...

  16. Depolymerization of organosolv lignin using doped porous metal oxides in supercritical methanol

    DEFF Research Database (Denmark)

    Warner, Genoa; Hansen, Thomas Søndergaard; Riisager, Anders

    2014-01-01

    conversion to methanol-soluble products, without char formation, were based on copper in combination with other dopants based on relatively earth-abundant metals. Nearly complete conversion of lignin to bio-oil composed of monomers and low-mass oligomers with high aromatic content was obtained in 6. h at 310......An isolated, solvent-extracted lignin from candlenut (Aleurites moluccana) biomass was subjected to catalytic depolymerization in the presence of supercritical methanol, using a range of porous metal oxides derived from hydrotalcite-like precursors. The most effective catalysts in terms of lignin...

  17. Wet in situ transesterification of spent coffee grounds with supercritical methanol for the production of biodiesel.

    Science.gov (United States)

    Son, Jeesung; Kim, Bora; Park, Jeongseok; Yang, Jeongwoo; Lee, Jae W

    2018-07-01

    This work introduces biodiesel production from wet spent coffee grounds (SCGs) with supercritical methanol without any pre-drying process. Supercritical methanol and subcritical water effectively produced biodiesel via in situ transesterification by inducing more porous SCG and enhancing the efficiency of lipid extraction and conversion. It was also found that space loading was one of the critical factors for biodiesel production. An optimal biodiesel yield of 10.17 wt% of dry SCG mass (86.33 w/w% of esterifiable lipids in SCG) was obtained at reaction conditions of 270 °C, 90 bars, methanol to wet SCG ratio 5:1, space loading 58.4 ml/g and reaction time 20 min. Direct use of wet SCG waste as feedstock for supercritical biodiesel production eliminates the conventional dying process and the need of catalyst and also reduces environmental problems caused by landfill accumulation. Copyright © 2018 Elsevier Ltd. All rights reserved.

  18. Co-deposition of Pt and ceria anode catalyst in supercritical carbon dioxide for direct methanol fuel cell applications

    International Nuclear Information System (INIS)

    You, Eunyoung; Guzmán-Blas, Rolando; Nicolau, Eduardo; Aulice Scibioh, M.; Karanikas, Christos F.; Watkins, James J.; Cabrera, Carlos R.

    2012-01-01

    Pt and mixed Pt-ceria catalysts were deposited onto gas diffusion layers using supercritical fluid deposition (SFD) to fabricate thin layer electrodes for direct methanol fuel cells. Dimethyl (1,5-cyclooctadiene) platinum (II) (CODPtMe 2 ) and tetrakis (2,2,6,6-tetramethyl 3,5-heptanedionato) cerium (IV) (Ce(tmhd) 4 ) were used as precursors. Hydrogen-assisted Pt deposition was performed in compressed carbon dioxide at 60 °C and 17.2 MPa to yield high purity Pt on carbon-black based gas diffusion layers. During the preparation of the mixed Pt-ceria catalyst, hydrogen reduction of CODPtMe 2 to yield Pt catalyzed the deposition of ceria from Ce(tmhd) 4 enabling co-deposition at 150 °C. The catalyst layers were characterized using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and scanning electron microscope-energy dispersive spectral (SEM-EDS) analyses. Their electrochemical performance toward methanol oxidation was examined in half cell mode using a three electrode assembly as well as in fuel cell mode. The thin layer electrodes formed via SFD exhibited higher performance in fuel cell operations compared to those prepared by the conventional brush-paint method. Furthermore, the Pt-ceria catalyst with an optimized composition exhibited greater methanol oxidation activity than pure platinum.

  19. Biodiesel II: A new concept of biodiesel production - transesterification with supercritical methanol

    Directory of Open Access Journals (Sweden)

    Skala Dejan U.

    2004-01-01

    Full Text Available Biodiesel is defined as a fuel that might be used as a pure biofuel or at high concentration in mineral oil derivatives, in accordance with specific quality standards for transport applications. The main raw material used for biodiesel production is rapeseed, which contains mono-unsaturated (about 60% and also, in a lower quantity, poly-unsaturated fatty acids (C 18:1 and C 18:3, as well as some amounts of undesired saturated fatty acids (palmitic and stearic acids. Other raw materials have also been used in the research and industrial production of biodiesel (palm-oil, sunflower-oil, soybean-oil, waste plant oil, animal fats, etc. The historical background of the biodiesel production, installed industrial capacities, as well as Directives of the European Parliament and of the Council (May 2003 regarding the promotion of the use of biofuels or other renewable fuels for transport are discussed in the first part of this article (Chem. Ind. 58 (2004. The second part focused on some new concepts and the future development of technology for biodiesel production based on the use of non-catalytic transesterification under supercritical conditions. A literature review, as well as original results based on the transesterification of animal fats, plant oil and used plant oil were discussed. Obtained results were compared with the traditional concept of transesterification based on base or acid catalysis. Experimental investigations of transesterification with supercritical methanol were performed in a 2 dm3 autoclave at 140 bar pressure and at 300°C with molar ratio of methanol to triglycerides of about 41. The degree of esterification strongly depends on the density of supercritical methanol and on the possibility of reaction occurring in one phase.

  20. In-situ Transesterification of Jatropha curcas L. Seeds for Biodiesel Production using Supercritical Methanol

    Directory of Open Access Journals (Sweden)

    Ishak M.A.M.

    2017-01-01

    Full Text Available In-situ supercritical methanol transesterification for production of biodiesel from Jatropha curcas L. (JCL seeds was successfully being carried out via batch-wise reactor system, under varying temperatures of 180 - 300 °C, pressures of 6 - 18 MPa, reaction time of 5 - 35 min and seeds-to-methanol ratio of 1:15 - 1:45 (w/v. In this study, the extracted oil obtained showed the presence of FAME referring as biodiesel, indicating that transesterification reaction had occurred during the extraction process. The results showed that the biodiesel yield was obtained at optimum conditions of 280 °C, 12 MPa, 30 min and 1:40 (w/v were 97.9%.

  1. Non Catalytic Transesterification of Vegetables Oil to Biodiesel in Sub-and Supercritical Methanol: A Kinetic’s Study

    OpenAIRE

    Nyoman Puspa Asri; Siti Machmudah; W. Wahyudiono; S. Suprapto; Kusno Budikarjono; Achmad Roesyadi; Motonobu Goto

    2013-01-01

    Non catalytic transesterification in sub and supercritical methanol have been used to produce biodiesel from palm oil and soybean oil. A kinetic study was done under reaction condition with temperature and time control. The experiments were carried out in a batch type reactor at reaction temperatures from 210 °C (subcritical condition) to 290 °C (the supercritical state) in the interval ranges of temperature of 20 °C and at various molar ratios of oil to methanol. The rate constants of the re...

  2. Techno-economic analysis of biodiesel production from Jatropha curcas via a supercritical methanol process

    International Nuclear Information System (INIS)

    Yusuf, N.N.A.N.; Kamarudin, S.K.

    2013-01-01

    Highlights: • This paper presents the techno-economic of a production of biodiesel from JCO. • The results obtained 99.96% of biodiesel with 96.49% of pure glycerol. • This proved that biodiesel from JCO is the least expensive compare to other resources. - Abstract: This paper presents the conceptual design and economic evaluation of a production of methyl esters (biodiesel) from Jatropha curcas oil (JCO) via a supercritical methanol process with glycerol as a by-product. The process consists of four major units: transesterification (PFR), methanol recovery (FT) and (DC1), recovery of glycerol (DEC), and biodiesel purification (DC2). The material and heat balance are also presented here. A biodiesel production of 40,000 tonnes-yr −1 is taken as case study. Biodiesel obtained from supercritical transesterification with Jatropha curcas oil as feedstock resulting in high purity methyl esters (99.96%) with almost pure glycerol (96.49%) obtained as by-product. The biodiesel can be sold at USD 0.78 kg −1 , while the manufacturing and capital investment costs are in the range of USD 25.39 million-year −1 and USD 9.41 million year −1 , respectively. This study proved that biodiesel from JCO is the least expensive with purities comparable to those found in other studies

  3. Radiolytic and electron-transfer reactions in supercritical CO2

    International Nuclear Information System (INIS)

    Bartels, D. M.; Dimitrijevic, N. M.; Jonah, C. D.; Takahashi, K.

    2000-01-01

    Using supercritical fluids as solvents is useful for both practical and theoretical reasons. It has been proposed to use supercritical CO 2 as a solvent for synthesis because it eliminates the air pollution arising from other solvents. The properties of supercritical fluids can be easily varied with only modest changes in temperature and density, so they provide a way of testing theories of chemical reactions. It has also been proposed to use supercritical fluids for the treatment of hazardous mixed waste. For these reasons the authors have studied the production of radiolytic species in supercritical CO 2 and have measured their reactivity as a function of density. They have shown that the C 2 O 4 + is formed. They also have shown that the electron transfer reactions of dimethylaniline to C 2 O 4 + and CO 2 (e - ) to benzoquinone are diffusion controlled over a considerable density range

  4. Comparative analysis of single-step and two-step biodiesel production using supercritical methanol on laboratory-scale

    International Nuclear Information System (INIS)

    Micic, Radoslav D.; Tomić, Milan D.; Kiss, Ferenc E.; Martinovic, Ferenc L.; Simikić, Mirko Ð.; Molnar, Tibor T.

    2016-01-01

    Highlights: • Single-step supercritical transesterification compared to the two-step process. • Two-step process: oil hydrolysis and subsequent supercritical methyl esterification. • Experiments were conducted in a laboratory-scale batch reactor. • Higher biodiesel yields in two-step process at milder reaction conditions. • Two-step process has potential to be cost-competitive with the single-step process. - Abstract: Single-step supercritical transesterification and two-step biodiesel production process consisting of oil hydrolysis and subsequent supercritical methyl esterification were studied and compared. For this purpose, comparative experiments were conducted in a laboratory-scale batch reactor and optimal reaction conditions (temperature, pressure, molar ratio and time) were determined. Results indicate that in comparison to a single-step transesterification, methyl esterification (second step of the two-step process) produces higher biodiesel yields (95 wt% vs. 91 wt%) at lower temperatures (270 °C vs. 350 °C), pressures (8 MPa vs. 12 MPa) and methanol to oil molar ratios (1:20 vs. 1:42). This can be explained by the fact that the reaction system consisting of free fatty acid (FFA) and methanol achieves supercritical condition at milder reaction conditions. Furthermore, the dissolved FFA increases the acidity of supercritical methanol and acts as an acid catalyst that increases the reaction rate. There is a direct correlation between FFA content of the product obtained in hydrolysis and biodiesel yields in methyl esterification. Therefore, the reaction parameters of hydrolysis were optimized to yield the highest FFA content at 12 MPa, 250 °C and 1:20 oil to water molar ratio. Results of direct material and energy costs comparison suggest that the process based on the two-step reaction has the potential to be cost-competitive with the process based on single-step supercritical transesterification. Higher biodiesel yields, similar or lower energy

  5. Fatty acid methyl esters synthesis from non-edible vegetable oils using supercritical methanol and methyl tert-butyl ether

    International Nuclear Information System (INIS)

    Lamba, Neha; Modak, Jayant M.; Madras, Giridhar

    2017-01-01

    Highlights: • FAMEs were synthesized from non-edible oils using supercritical MeOH and MTBE. • Effect of time, temperature, pressure and molar ratio on conversions was studied. • Rate constants of reaction with methanol and MTBE differ by an order of magnitude. • Non-catalytic supercritical reactions are one order faster than acid catalyzed synthesis. - Abstract: Fatty acid methyl esters (FAMEs) are useful as biodiesel and have environmental benefits compared to conventional diesel. In this study, these esters were synthesized non-catalytically from non-edible vegetable oils: neem oil and mahua oil with two different methylating agents: methanol and methyl tert-butyl ether (MTBE). The effects of temperature, pressure, time and molar ratio on the conversion of triglycerides were studied. The temperature was varied in the range of 523–723 K with molar ratios upto 50:1 and a reaction time of upto 150 min. Conversion of neem and mahua oil to FAMEs with supercritical methanol was found to be 83% in 15 min and 99% in 10 min, respectively at 698 K. Further, a conversion of 46% of mahua oil and 59% of neem oil was obtained in 15 min at 723 K using supercritical MTBE. The rate constants evaluated using pseudo first order reaction kinetics were in the range of 4.7 × 10"−"6 to 1.0 × 10"−"3 s"−"1 for the investigated range of temperatures. The activation energies obtained were in the range of 62–113 kJ/mol for the reaction systems investigated. The supercritical synthesis was found to be superior to the catalytic synthesis of the corresponding FAMEs.

  6. Electron transport in ethanol & methanol absorbed defected graphene

    Science.gov (United States)

    Dandeliya, Sushmita; Srivastava, Anurag

    2018-05-01

    In the present paper, the sensitivity of ethanol and methanol molecules on surface of single vacancy defected graphene has been investigated using density functional theory (DFT). The changes in structural and electronic properties before and after adsorption of ethanol and methanol were analyzed and the obtained results show high adsorption energy and charge transfer. High adsorption happens at the active site with monovacancy defect on graphene surface. Present work confirms that the defected graphene increases the surface reactivity towards ethanol and methanol molecules. The presence of molecules near the active site affects the electronic and transport properties of defected graphene which makes it a promising choice for designing methanol and ethanol sensor.

  7. Non Catalytic Transesterification of Vegetables Oil to Biodiesel in Sub-and Supercritical Methanol: A Kinetic’s Study

    Directory of Open Access Journals (Sweden)

    Nyoman Puspa Asri

    2013-03-01

    Full Text Available Non catalytic transesterification in sub and supercritical methanol have been used to produce biodiesel from palm oil and soybean oil. A kinetic study was done under reaction condition with temperature and time control. The experiments were carried out in a batch type reactor at reaction temperatures from 210 °C (subcritical condition to 290 °C (the supercritical state in the interval ranges of temperature of 20 °C and at various molar ratios of oil to methanol. The rate constants of the reaction were determined by employing a simple method, with the overall chemical reaction followed the pseudo-first–order reaction. Based on the results, the rate constants of vegetables oil were significantly influenced by reaction temperature, which were gradually increased at subcritical temperature, but sharply increased in the supercritical state. However, the rate constants of soybean oil were slightly higher than that of palm oil. The activation energy for transesterification of soybean oil was 89.32 and 79.05 kJ/mole for palm oil. Meanwhile, the frequency factor values of both oils were 72462892 and 391210 min-1, respectively. The rate reaction for both of oil were expressed as -rTG = 72462892 exp(-89.32/RTCTG for soybean oil and -rTG = 391210 exp(-79.05/RTCTG for palm oil. © 2013 BCREC UNDIP. All rights reservedReceived: 18th October 2012; Revised: 14th December 2012; Accepted: 16th December 2012[How to Cite: N.P. Asri, S. Machmudah, W. Wahyudiono, S. Suprapto, K. Budikarjono, A. Roesyadi, M. Goto, (2013. Non Catalytic Transesterification of Vegetables Oil to Biodiesel in Sub-and Supercritical Methanol: A Kinetic’s Study. Bulletin of Chemical Reaction Engineering & Catalysis, 7 (3: 215-223. (doi:10.9767/bcrec.7.3.4060.215-223][Permalink/DOI: http://dx.doi.org/10.9767/bcrec.7.3.4060.215-223 ] View in  |

  8. High-yield production of biodiesel by non-catalytic supercritical methanol transesterification of crude castor oil (Ricinus communis)

    International Nuclear Information System (INIS)

    Román-Figueroa, Celián; Olivares-Carrillo, Pilar; Paneque, Manuel; Palacios-Nereo, Francisco Javier; Quesada-Medina, Joaquín

    2016-01-01

    The synthesis of biodiesel from crude castor oil in a catalyst-free process using supercritical methanol in a batch reactor was investigated, studying the evolution of intermediate products as well as the conversion of triglycerides and the yield of FAMEs (fatty acid methyl esters) (biodiesel). Experiments were carried out in a temperature range of 250–350 °C (10–43 MPa) at reaction times of 15–90 min for a methanol-to-oil molar ratio of 43:1. Maintaining thermal stability of biodiesel is one of the most important concerns in high-yield supercritical biodiesel production. Hence, thermal decomposition degree of FAMEs was also investigated in different reaction conditions. The maximum yield of FAMEs (96.5%) was obtained at 300 °C (21 MPa) and 90 min. Under these conditions, the conversion of triglycerides was complete, the yield of intermediate products was low (3.29 and 1.41% for monoglycerides and diglycerides, respectively), and thermal decomposition of FAMEs did not occur. The maximum degree of thermal decomposition (80.9%) was produced at 350 °C (43 MPa) and 90 min. Methyl ricinoleate, whose fatty acid chain was the most abundant (88.09 mol%) in castor oil, was very unstable above 300 °C and 60 min, leading to low yields of FAMEs under these conditions. - Highlights: • Supercritical synthesis of biodiesel from crude castor oil was investigated. • Supercritical methanolysis of crude castor oil reached a high yield of FAMEs. • Ricinoleic acid methyl ester was very unstable above 300 °C and 60 min reaction.

  9. Continuous production of biofuel from refined and used palm olein oil with supercritical methanol at a low molar ratio

    International Nuclear Information System (INIS)

    Sakdasri, Winatta; Sawangkeaw, Ruengwit; Ngamprasertsith, Somkiat

    2015-01-01

    Highlights: • Continuous production of biofuel in SCM at low molar ratio was studied. • The actual density of mixture was applied to calculate residence times. • The maximum FAME of 80–90% was observed for refined and used palm oils. • The glycerol–methanol reaction showed a positive effect in fuel yield. - Abstract: The high energy consumption and high environmental impact in the supercritical methanol (SCM) process primarily originates from the preheating of reactants and the recovery of excess alcohols. This work demonstrated the synthesis of biofuel using a lowered methanol to oil molar ratio of 12:1, instead of the 40:1–42:1 ratios that are commonly employed in conventional SCM. The apparent density of the reacting mixture was measured and applied to accurately calculate residence times in a continuous reactor. The effects of residence time were considered from 10 to 25 min. The results revealed that excessive residence times reduced the ester content, especially for unsaturated esters, in the resulting biofuel. A residence time of 20 min was recommended to simultaneously achieve a maximum ester content of 90% and a triglyceride conversion of up to 99%. Used palm olein oil with high free fatty acid (4.56 wt.%) can be employed as a feedstock and give a maximum ester content of 80%. In addition, the side reaction between glycerol and methanol at 400 °C and 15 MPa showed a positive effect in increasing fuel yield by 2%–7%

  10. A whole biodiesel conversion process combining isolation, cultivation and in situ supercritical methanol transesterification of native microalgae.

    Science.gov (United States)

    Jazzar, Souhir; Quesada-Medina, Joaquín; Olivares-Carrillo, Pilar; Marzouki, Mohamed Néjib; Acién-Fernández, Francisco Gabriel; Fernández-Sevilla, José María; Molina-Grima, Emilio; Smaali, Issam

    2015-08-01

    A coupled process combining microalgae production with direct supercritical biodiesel conversion using a reduced number of operating steps is proposed in this work. Two newly isolated native microalgae strains, identified as Chlorella sp. and Nannochloris sp., were cultivated in both batch and continuous modes. Maximum productivities were achieved during continuous cultures with 318mg/lday and 256mg/lday for Chlorella sp. and Nannochloris sp., respectively. Microalgae were further characterized by determining their photosynthetic performance and nutrient removal efficiency. Biodiesel was produced by catalyst-free in situ supercritical methanol transesterification of wet unwashed algal biomass (75wt.% of moisture). Maximum biodiesel yields of 45.62wt.% and 21.79wt.% were reached for Chlorella sp. and Nannochloris sp., respectively. The analysis of polyunsaturated fatty acids of Chlorella sp. showed a decrease in their proportion when comparing conventional and supercritical transesterification processes (from 37.4% to 13.9%, respectively), thus improving the quality of the biodiesel. Copyright © 2015 Elsevier Ltd. All rights reserved.

  11. Upgrading pyrolysis bio-oil to biofuel over bifunctional Co-Zn/HZSM-5 catalyst in supercritical methanol

    International Nuclear Information System (INIS)

    Cheng, Shouyun; Wei, Lin; Julson, James; Muthukumarappan, Kasiviswanathan; Kharel, Parashu Ram

    2017-01-01

    Highlights: • Integration of Co-Zn/HZSM-5 and supercritical methanol was used for bio-oil hydrodeoxygenation. • Co-Zn/HZSM-5 exhibited higher effectiveness than Co/HZSM-5 or Zn/HZSM-5. • 15%Co5%Zn/HZSM-5 produced biofuel with the highest hydrocarbons content at 35.33%. • Loading of Co and/or Zn did not change crystalline structure of HZSM-5. • Hydrogenation and esterification are main reactions in bio-oil hydrodeoxygenation. - Abstract: The role of catalyst is essential in processes of upgrading biomass pyrolysis bio-oil into hydrocarbon biofuel. While the majority of heterogeneous catalytic processes are conducted in the presence of gas (nearly ideal) or liquid phase, a growing number of processes are utilizing supercritical fluids (SCFs) as reaction media. Although hydrodeoxygenation (HDO) is proven a promising process for pyrolysis bio-oil upgrading to hydrocarbon biofuel, catalyst efficiency remains a challenge. Integrating heterogeneous catalysts with SCFs in a bio-oil HDO process was investigated in this study. Bifunctional Co-Zn/HZSM-5 catalysts were firstly used to upgrade bio-oil to biofuel in supercritical methanol. The loading of Co and Zn did not change HZSM-5 crystalline structure. Physicochemical properties of biofuel produced by Co and/or Zn loaded HZSM-5 catalysts such as water content, total acid number, viscosity and higher heating value improved. Bimetallic Co-Zn/HZSM-5 catalysts showed enhanced reactions of decarboxylation and decarbonylation that resulted in higher yields of CO and CO 2 . Bimetallic Co-Zn/HZSM-5 catalysts were more effective for bio-oil HDO than monometallic Co/HZSM-5 or Zn/HZSM-5 catalyst , which was attributed to the synergistic effect of Co and Zn on HZSM-5 support. Bimetallic Co-Zn/HZSM-5 catalysts increased biofuel yields and hydrocarbons contents in biofuels in comparison with monometallic Co/HZSM-5 and Zn/HZSM-5 catalysts. 5%Co15%Zn/HZSM-5 catalyst generated the highest biofuel yield at 22.13 wt.%, and 15%Co5

  12. Oxidation of hazardous waste in supercritical water: A comparison of modeling and experimental results for methanol destruction

    International Nuclear Information System (INIS)

    Butler, P.B.; Bergan, N.E.; Bramlette, T.T.; Pitz, W.J.; Westbrook, C.K.

    1991-01-01

    Recent experiments at Sandia National Laboratories conducted in conjunction with MODEC Corporation have demonstrated successful clean- up of contaminated water in a supercritical water reactor. These experiments targeted wastes of interest to Department of Energy production facilities. In this paper we present modeling and experimental results for a surrogate waste containing 98% water, 2% methanol, and parts per million of chlorinated hydrocarbons and laser dyes. Our initial modeling results consider only methanol and water. Experimental data are available for inlet and outlet conditions and axial temperature profiles along the outside reactor wall. The purpose of our model is to study the chemical and physical processes inside the reactor. We are particularly interested in the parameters that control the location of the reaction zone. The laboratory-scale reactor operates at 25 MPa., between 300 K and 900 K; it is modeled as a plug-flow reactor with a specified temperature profile. We use Chemkin Real-Gas to calculate mixture density, with the Peng-Robinson equation of state. The elementary reaction set for methanol oxidation and reactions of other C 1 and C 2 hydrocarbons is based on previous models for gas-phase kinetics. Results from our calculations show that the methanol is 99.9% destroyed at 1/3 the total reactor length. Although we were not able to measure composition of the fluid inside the experimental reactor, this prediction occurs near the location of the highest reactor temperature. This indicates that the chemical reaction is triggered by thermal effects, not kinetic rates. Results from ideal-gas calculations show nearly identical chemical profiles inside the reactor in dimensionless distance. However, reactor residence times are overpredicted by nearly 150% using an ideal-gas assumption. Our results indicate that this oxidation process can be successfully modeled using gas-phase chemical mechanisms. 23 refs., 8 figs

  13. Economic and environmental performance of oil transesterification in supercritical methanol at different reaction conditions: Experimental study with a batch reactor

    International Nuclear Information System (INIS)

    Tomic, Milan; Micic, Radoslav; Kiss, Ferenc; Dedovic, Nebojsa; Simikic, Mirko

    2015-01-01

    Highlights: • Influence of reaction parameters on FAME yields has been investigated. • The highest yield (93%) was achieved after 15 min at 350 °C and 12 MPa. • Models which predict with high certainty yields at different reaction conditions. • Economic and environmental performance of supercritical transesterification. • The lowest costs and impacts are always achieved at the highest yields. - Abstract: This study aims to investigate the influence of various reaction parameters (temperatures, working pressures and reaction time) on biodiesel yields and environmental and economic performance of rapeseed oil transesterification in supercritical methanol. Experiments were carried out in a laboratory-scale batch reactor. Results were statistically analysed and multiple regression models which describe and predict biodiesel yields with high certainty at different reaction conditions were provided. The highest biodiesel yield (93 wt%) was achieved at 350 °C and 12 MPa after 15 min of reaction. The lowest direct costs and life cycle environmental impacts (in terms of GHG emissions and fossil energy demand) are achieved at the highest yield due to the lowest oil consumption per unit of biodiesel produced. The results of sensitivity analysis showed that even at significantly lower oil feedstock prices this observation stands firm

  14. Attractive and repulsive interactions among methanol molecules in supercritical state investigated by Raman spectroscopy and perturbed hard-sphere theory.

    Science.gov (United States)

    Saitow, Ken-ichi; Sasaki, Jungo

    2005-03-08

    The short-range structure of supercritical methanol (CH(3)OH) is investigated by measuring the spontaneous Raman spectra of the C-O stretching mode. The spectra are obtained at a reduced temperature, T(r)=T/T(c)=1.02 (522.9 K), which permits the neat fluid to be studied isothermally as a function of density. As the density increases, the spectral peaks shift toward the lower energy side and the spectra broaden. In the supercritical region, the amount of shifting shows nonlinear density dependence and the width becomes anomalously large. We use the perturbed hard-sphere model to analyze these density dependencies along the vibrational coordinate. The amount of shifting is decomposed into attractive and repulsive components, and the changes in attractive and repulsive energies are evaluated as functions of density and packing fraction, both of which are continuously varied by a factor of 120. Here we show that the shift amount consists principally of the attractive component at all densities, since the attractive energy is about eight times the repulsive energy. The density dependence of the widths is analyzed by calculating homogeneous and inhomogeneous widths as a function of density. The results show that, although vibrational dephasing and density inhomogeneity contribute similarly to the width at low and middle densities, at high density the main contributor turns out to be the vibrational dephasing. We estimate the local density enhancements of supercritical CH(3)OH as function of bulk density by two methods. The results of these analyses show common features, and both the estimated local density enhancements of CH(3)OH are considerably larger than the local density enhancements of simple fluids, i.e., those having nonhydrogen bonding. It is revealed that the local density of supercritical CH(3)OH is 40%-60% greater than the local densities of the simple fluids. We also estimate the local density fluctuation using the obtained values of attractive shift

  15. Substantial rate enhancements of the esterification reaction of phthalic anhydride with methanol at high pressure and using supercritical CO2 as a co-solvent in a glass microreactor

    NARCIS (Netherlands)

    Benito-Lopez, F.; Tiggelaar, Roald M.; Salblut, K.; Huskens, Jurriaan; Egberink, Richard J.M.; Reinhoudt, David; Gardeniers, Johannes G.E.; Verboom, Willem

    2007-01-01

    The esterification reaction of phthalic anhydride with methanol was performed at different temperatures in a continuous flow glass microreactor at pressures up to 110 bar and using supercritical CO2 as a co-solvent. The design is such that supercritical CO2 can be generated inside the microreactor.

  16. Excess electrons in methanol clusters: Beyond the one-electron picture

    Science.gov (United States)

    Pohl, Gábor; Mones, Letif; Turi, László

    2016-10-01

    We performed a series of comparative quantum chemical calculations on various size negatively charged methanol clusters, ("separators=" CH 3 OH ) n - . The clusters are examined in their optimized geometries (n = 2-4), and in geometries taken from mixed quantum-classical molecular dynamics simulations at finite temperature (n = 2-128). These latter structures model potential electron binding sites in methanol clusters and in bulk methanol. In particular, we compute the vertical detachment energy (VDE) of an excess electron from increasing size methanol cluster anions using quantum chemical computations at various levels of theory including a one-electron pseudopotential model, several density functional theory (DFT) based methods, MP2 and coupled-cluster CCSD(T) calculations. The results suggest that at least four methanol molecules are needed to bind an excess electron on a hydrogen bonded methanol chain in a dipole bound state. Larger methanol clusters are able to form stronger interactions with an excess electron. The two simulated excess electron binding motifs in methanol clusters, interior and surface states, correlate well with distinct, experimentally found VDE tendencies with size. Interior states in a solvent cavity are stabilized significantly stronger than electron states on cluster surfaces. Although we find that all the examined quantum chemistry methods more or less overestimate the strength of the experimental excess electron stabilization, MP2, LC-BLYP, and BHandHLYP methods with diffuse basis sets provide a significantly better estimate of the VDE than traditional DFT methods (BLYP, B3LYP, X3LYP, PBE0). A comparison to the better performing many electron methods indicates that the examined one-electron pseudopotential can be reasonably used in simulations for systems of larger size.

  17. Passive direct methanol fuel cells for portable electronic devices

    International Nuclear Information System (INIS)

    Achmad, F.; Kamarudin, S.K.; Daud, W.R.W.; Majlan, E.H.

    2011-01-01

    Due to the increasing demand for electricity, clean, renewable energy resources must be developed. Thus, the objective of the present study was to develop a passive direct methanol fuel cell (DMFC) for portable electronic devices. The power output of six dual DMFCs connected in series with an active area of 4 cm 2 was approximately 600 mW, and the power density of the DMFCs was 25 mW cm -2 . The DMFCs were evaluated as a power source for mobile phone chargers and media players. The results indicated that the open circuit voltage of the DMFC was between 6.0 V and 6.5 V, and the voltage under operating conditions was 4.0 V. The fuel cell was tested on a variety of cell phone chargers, media players and PDAs. The cost of energy consumption by the proposed DMFC was estimated to be USD 20 W -1 , and the cost of methanol is USD 4 kW h. Alternatively, the local conventional electricity tariff is USD 2 kW h. However, for the large-scale production of electronic devices, the cost of methanol will be significantly lower. Moreover, the electricity tariff is expected to increase due to the constraints of fossil fuel resources and pollution. As a result, DMFCs will become competitive with conventional power sources.

  18. Optimization of non-catalytic transesterification of tobacco (Nicotiana tabacum) seed oil using supercritical methanol to biodiesel production

    International Nuclear Information System (INIS)

    García-Martínez, Nuria; Andreo-Martínez, Pedro; Quesada-Medina, Joaquín; Pérez de los Ríos, Antonia Pérez; Chica, Antonio; Beneito-Ruiz, Rubén; Carratalá-Abril, Juan

    2017-01-01

    Highlights: • Biodiesel from tobacco oil was produced by non-catalytic supercritical methanolysis. • Maximum experimental yield of FAMEs (92.8%) was reached at 300 °C and 90 min. • Optimal conditions by RSM (303.4 °C and 90 min) predicted a maximum FAME yield of 91.1%. • Thermal decomposition of biodiesel was observed above 325 °C and 60 min of reaction. • Glycerol generated at 300 °C and 90 min was degraded and incorporated to the biodiesel. - Abstract: The biodiesel production from non-edible oils has high potential as renewable and ecological fuel. Few researches have been conducted to date on the production of biodiesel from tobacco (Nicotiana tabacum) seed oil. The aim of this study was to optimize the biodiesel production from this crude oil by non-catalytic supercritical methanolysis using response surface methodology (RSM). Triglyceride conversion, total and individual FAME yield, monoglyceride and diglyceride yield, and thermal decomposition degree of biodiesel were determined in the temperature and reaction time ranges of 250–350 °C (12–43 MPa) and 15–90 min, respectively, at a fixed methanol-to-oil molar ratio of 43:1. According to the RSM, the optimal conditions were 303.4 °C and 90 min, reaching a predicted maximum FAME yield of 91.1 ± 3.2 mol%. This maximum was very close to that obtained experimentally (92.8 ± 2.1 mol%) at 300 °C and 90 min. Decomposition of biodiesel became evident at 325 °C and 60 min of reaction due to the thermal instability of unsaturated methyl esters (methyl linoleate and oleate). The biodiesel obtained in the best experimental reaction conditions (300 °C and 90 min), where no thermal decomposition of FAMEs was observed, contained most of the byproduct glycerol generated, which was degraded and incorporated to the product. This biodiesel basically failed to meet the content of FAMEs as required by the standard EN 14214, the content of monoglycerides and total glycerol, and the acid value, being a

  19. Methanol as an alternative electron donor in chain elongation for butyrate and caproate formation

    OpenAIRE

    Chen, W.S.; Ye, Y.; Steinbusch, K.J.J.; Strik, D.P.B.T.B.; Buisman, C.J.N.

    2016-01-01

    Chain elongation is an emerging mixed culture biotechnology converting acetate into valuable biochemicals by using ethanol as an external electron donor. In this study we proposed to test another potential electron donor, methanol, in chain elongation. Methanol can be produced through the thermochemical conversion of lignocellulosic biowaste. Use of methanol in chain elongation integrates the lignocellulosic feedstocks and the thermochemical platform technologies into chain elongation. After ...

  20. Methanol as an alternative electron donor in chain elongation for butyrate and caproate formation

    NARCIS (Netherlands)

    Chen, W.S.; Ye, Y.; Steinbusch, K.J.J.; Strik, D.P.B.T.B.; Buisman, C.J.N.

    2016-01-01

    Chain elongation is an emerging mixed culture biotechnology converting acetate into valuable biochemicals by using ethanol as an external electron donor. In this study we proposed to test another potential electron donor, methanol, in chain elongation. Methanol can be produced through the

  1. Solvation in supercritical water

    International Nuclear Information System (INIS)

    Cochran, H.D.; Cummings, P.T.; Karaborni, S.

    1991-01-01

    The aim of this work is to determine the solvation structure in supercritical water composed with that in ambient water and in simple supercritical solvents. Molecular dynamics studies have been undertaken of systems that model ionic sodium and chloride, atomic argon, and molecular methanol in supercritical aqueous solutions using the simple point charge model of Berendsen for water. Because of the strong interactions between water and ions, ionic solutes are strongly attractive in supercritical water, forming large clusters of water molecules around each ion. Methanol is found to be a weakly-attractive solute in supercritical water. The cluster of excess water molecules surrounding a dissolved ion or polar molecule in supercritical aqueous solutions is comparable to the solvent clusters surrounding attractive solutes in simple supercritical fluids. Likewise, the deficit of water molecules surrounding a dissolved argon atom in supercritical aqueous solutions is comparable to that surrounding repulsive solutes in simple supercritical fluids. The number of hydrogen bonds per water molecule in supercritical water was found to be about one third the number in ambient water. The number of hydrogen bonds per water molecule surrounding a central particle in supercritical water was only mildly affected by the identify of the central particle--atom, molecule, or ion. These results should be helpful in developing a qualitative understanding of important processes that occur in supercritical water. 29 refs., 6 figs

  2. Sub/supercritical carbon dioxide induced phase switching for the reaction and separation in ILs/methanol

    Directory of Open Access Journals (Sweden)

    Jiayu Xin

    2016-07-01

    Full Text Available Separation of products from ionic liquid (IL solvents is one of the main challenges that hinder their utilizations. In this study, the production of γ-valerolactone (GVL by selective hydrogenation of α-angelica lactone (AL and separation of the products from the IL solvent were carried out by using subcritical CO2 as a “switch” at room temperature. After the mixture was separated into two phases by subcritical CO2, AL and nano Pd/C catalyst were only found in the lower IL-rich phase, GVL was produced with quantitative yield and enriched in the upper methanol-rich phase. Pure GVL can be obtained by depressurizing to release CO2 and evaporation to remove methanol of the upper phase, the lower phase containing IL, catalyst and methanol can be recycled for the next reaction. The strategy may provide a new approach to produce and separate products from IL solvents at mild conditions. Keywords: Separation, Ionic liquids, Selective hydrogenation, Mild condition, Subcritical CO2

  3. Experimental investigations of interaction of supercritical electron beams with plasma

    International Nuclear Information System (INIS)

    Chupikov, P.T.; Medvedev, D.V.; Onishchenko, I.N.; Panasenko, B.D.; Faehl, R.J.

    2002-01-01

    The first section of the collective ions acceleration based on simultaneous temporal and spatial modulation of relativistic electron beam (REB) was studied experimentally. The virtual cathode was originated in the electrodynamic structure consisting of two tubes with different diameters (jump of electrodynamics) by REB, produced in magnetically insulated diode. At plasma assistance the low-frequency oscillations of REB current and the low-frequency microwave radiation were obtained due to the virtual cathode periodical relaxation in the processes of charge compensation by ionized residual gas

  4. Electron mobility in supercritical pentanes as a function of density and temperature

    International Nuclear Information System (INIS)

    Itoh, Kengo; Nakagawa, Kazumichi; Nishikawa, Masaru

    1988-01-01

    The excess electron mobility in supercritical n-, iso- and neopentane was measured isothermally as a function of density. The density-normalized mobility μN in all three isomers goes through a minimum at a density below the respective critical densities, and the mobility is quite temperature-dependent in this region, then goes through a minimum. The μN behavior around the minimum in n-pentane is well accounted for by the Cohen-Lekner model with the structure factor S(K) estimated from the speed of sound, while that in iso- and neopentane is not. (author)

  5. Methanol as electron donor for thermophilic biological sulfate and sulfite reduction

    OpenAIRE

    Weijma, J.

    2000-01-01

    Sulfur oxyanions (e.g. sulfate, sulfite) can be removed from aqueous waste- and process streams by biological reduction with a suitable electron donor to sulfide, followed by partial chemical or biological oxidation of sulfide to elemental sulfur. The aim of the research described in this thesis was to make this biological process more broadly applicable for desulfurization of flue-gases and ground- and wastewaters by using the cheap chemical methanol as electron donor for the reduct...

  6. Total electron scattering cross sections for methanol and ethanol at intermediate energies

    International Nuclear Information System (INIS)

    Silva, D G M; Tejo, T; Lopes, M C A; Muse, J; Romero, D; Khakoo, M A

    2010-01-01

    Absolute total cross section (TCS) measurements of electron scattering from gaseous methanol and ethanol molecules are reported for impact energies from 60 to 500 eV, using the linear transmission method. The attenuation of intensity of a collimated electron beam through the target volume is used to determine the absolute TCS for a given impact energy, using the Beer-Lambert law to first approximation. Besides these experimental measurements, we have also determined TCS using the additivity rule.

  7. Chaos control in an electron beam with the supercritical current in the hydrodynamic model of the Pierce diode

    International Nuclear Information System (INIS)

    Koronovskij, A.A.; Rempen, I.S.; Khramov, A.E.

    2003-01-01

    The possibility of controlling the chaos in the electron beam with the supercritical current in the hydrodynamic model of the Pierce diode through the continuous feedback; the methodology of controlling the chaotic dynamics through stabilization of the unstable equilibrium state in the distributed active medium is proposed [ru

  8. Antimicrobial Activities of Methanol, Ethanol and Supercritical CO2 Extracts of Philippine Piper betle L. on Clinical Isolates of Gram Positive and Gram Negative Bacteria with Transferable Multiple Drug Resistance.

    Directory of Open Access Journals (Sweden)

    Demetrio L Valle

    Full Text Available Piper betle L. has traditionally been used in alternative medicine in different countries for various therapeutic purposes, including as an anti-infective agent. However, studies reported in the literature are mainly on its activities on drug susceptible bacterial strains. This study determined the antimicrobial activities of its ethanol, methanol, and supercritical CO2 extracts on clinical isolates of multiple drug resistant bacteria which have been identified by the Infectious Disease Society of America as among the currently more challenging strains in clinical management. Assay methods included the standard disc diffusion method and the broth microdilution method for the determination of the minimum inhibitory concentration (MIC and the minimum bactericidal concentrations (MBC of the extracts for the test microorganisms. This study revealed the bactericidal activities of all the P. betle leaf crude extracts on methicillin-resistant Staphylococcus aureus (MRSA, vancomycin-resistant Enterococcus (VRE, extended spectrum β-lactamase-producing Enterobacteriaceae, carbapenem-resistant Enterobacteriaceae, and metallo-β-lactamase-producing Pseudomonas aeruginosa and Acinetobacter baumannii, with minimum bactericidal concentrations that ranged from 19μg/ml to 1250 μg/ml. The extracts proved to be more potent against the Gram positive MRSA and VRE than for the Gram negative test bacteria. VRE isolates were more susceptible to all the extracts than the MRSA isolates. Generally, the ethanol extracts proved to be more potent than the methanol extracts and supercritical CO2 extracts as shown by their lower MICs for both the Gram positive and Gram negative MDRs. MTT cytotoxicity assay showed that the highest concentration (100 μg/ml of P. betle ethanol extract tested was not toxic to normal human dermal fibroblasts (HDFn. Data from the study firmly established P. betle as an alternative source of anti-infectives against multiple drug resistant

  9. Antimicrobial Activities of Methanol, Ethanol and Supercritical CO2 Extracts of Philippine Piper betle L. on Clinical Isolates of Gram Positive and Gram Negative Bacteria with Transferable Multiple Drug Resistance.

    Science.gov (United States)

    Valle, Demetrio L; Cabrera, Esperanza C; Puzon, Juliana Janet M; Rivera, Windell L

    2016-01-01

    Piper betle L. has traditionally been used in alternative medicine in different countries for various therapeutic purposes, including as an anti-infective agent. However, studies reported in the literature are mainly on its activities on drug susceptible bacterial strains. This study determined the antimicrobial activities of its ethanol, methanol, and supercritical CO2 extracts on clinical isolates of multiple drug resistant bacteria which have been identified by the Infectious Disease Society of America as among the currently more challenging strains in clinical management. Assay methods included the standard disc diffusion method and the broth microdilution method for the determination of the minimum inhibitory concentration (MIC) and the minimum bactericidal concentrations (MBC) of the extracts for the test microorganisms. This study revealed the bactericidal activities of all the P. betle leaf crude extracts on methicillin-resistant Staphylococcus aureus (MRSA), vancomycin-resistant Enterococcus (VRE), extended spectrum β-lactamase-producing Enterobacteriaceae, carbapenem-resistant Enterobacteriaceae, and metallo-β-lactamase-producing Pseudomonas aeruginosa and Acinetobacter baumannii, with minimum bactericidal concentrations that ranged from 19μg/ml to 1250 μg/ml. The extracts proved to be more potent against the Gram positive MRSA and VRE than for the Gram negative test bacteria. VRE isolates were more susceptible to all the extracts than the MRSA isolates. Generally, the ethanol extracts proved to be more potent than the methanol extracts and supercritical CO2 extracts as shown by their lower MICs for both the Gram positive and Gram negative MDRs. MTT cytotoxicity assay showed that the highest concentration (100 μg/ml) of P. betle ethanol extract tested was not toxic to normal human dermal fibroblasts (HDFn). Data from the study firmly established P. betle as an alternative source of anti-infectives against multiple drug resistant bacteria.

  10. Electron-Stimulated Desorption of Positive Ions from Methanol Adsorbed on a Solid Ar Substrate

    Science.gov (United States)

    Kawanowa, H.; Hanatani, K.; Gotoh, Y.; Souda, R.

    Electron-stimulated desorption (ESD) of positive ions from weakly physisorbed molecules has been investigated. From methanol adsorbed on a solid Ar substrate, the protonated cluster ions of the type H+(CH3OH)n (n = 1 - 4) are emitted, together with the fragment ions such as CHn+ (n = 0 - 3), H3O+, CHO+, CH3O+, etc. The yields of these ions are markedly enhanced at the smallest coverage and decay steeply with increasing coverage. Coulomb explosion between valence holes confined in adsorbed nanoclusters is responsible for the enhanced ion yields. Very few ions except for H+ are emitted from a thick layer as well as nanoclusters adsorbed directly on a metal substrate due to the delocalization of valence holes.

  11. Dynamics of electron solvation in methanol: Excited state relaxation and generation by charge-transfer-to-solvent

    International Nuclear Information System (INIS)

    Elkins, Madeline H.; Williams, Holly L.; Neumark, Daniel M.

    2015-01-01

    The charge-transfer-to-solvent dynamics (CTTS) and excited state relaxation mechanism of the solvated electron in methanol are studied by time-resolved photoelectron spectroscopy on a liquid methanol microjet by means of two-pulse and three-pulse experiments. In the two-pulse experiment, CTTS excitation is followed by a probe photoejection pulse. The resulting time-evolving photoelectron spectrum reveals multiple time scales characteristic of relaxation and geminate recombination of the initially generated electron which are consistent with prior results from transient absorption. In the three-pulse experiment, the relaxation dynamics of the solvated electron following electronic excitation are measured. The internal conversion lifetime of the excited electron is found to be 130 ± 40 fs, in agreement with extrapolated results from clusters and the non-adiabatic relaxation mechanism

  12. Dynamics of electron solvation in methanol: Excited state relaxation and generation by charge-transfer-to-solvent

    Science.gov (United States)

    Elkins, Madeline H.; Williams, Holly L.; Neumark, Daniel M.

    2015-06-01

    The charge-transfer-to-solvent dynamics (CTTS) and excited state relaxation mechanism of the solvated electron in methanol are studied by time-resolved photoelectron spectroscopy on a liquid methanol microjet by means of two-pulse and three-pulse experiments. In the two-pulse experiment, CTTS excitation is followed by a probe photoejection pulse. The resulting time-evolving photoelectron spectrum reveals multiple time scales characteristic of relaxation and geminate recombination of the initially generated electron which are consistent with prior results from transient absorption. In the three-pulse experiment, the relaxation dynamics of the solvated electron following electronic excitation are measured. The internal conversion lifetime of the excited electron is found to be 130 ± 40 fs, in agreement with extrapolated results from clusters and the non-adiabatic relaxation mechanism.

  13. Dynamics of electron solvation in methanol: Excited state relaxation and generation by charge-transfer-to-solvent

    Energy Technology Data Exchange (ETDEWEB)

    Elkins, Madeline H.; Williams, Holly L. [Department of Chemistry, University of California, Berkeley, California 94720 (United States); Neumark, Daniel M. [Department of Chemistry, University of California, Berkeley, California 94720 (United States); Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States)

    2015-06-21

    The charge-transfer-to-solvent dynamics (CTTS) and excited state relaxation mechanism of the solvated electron in methanol are studied by time-resolved photoelectron spectroscopy on a liquid methanol microjet by means of two-pulse and three-pulse experiments. In the two-pulse experiment, CTTS excitation is followed by a probe photoejection pulse. The resulting time-evolving photoelectron spectrum reveals multiple time scales characteristic of relaxation and geminate recombination of the initially generated electron which are consistent with prior results from transient absorption. In the three-pulse experiment, the relaxation dynamics of the solvated electron following electronic excitation are measured. The internal conversion lifetime of the excited electron is found to be 130 ± 40 fs, in agreement with extrapolated results from clusters and the non-adiabatic relaxation mechanism.

  14. Electronic modification of Pt via Ti and Se as tolerant cathodes in air-breathing methanol microfluidic fuel cells.

    Science.gov (United States)

    Ma, Jiwei; Habrioux, Aurélien; Morais, Cláudia; Alonso-Vante, Nicolas

    2014-07-21

    We reported herein on the use of tolerant cathode catalysts such as carbon supported Pt(x)Ti(y) and/or Pt(x)Se(y) nanomaterials in an air-breathing methanol microfluidic fuel cell. In order to show the improvement of mixed-reactant fuel cell (MRFC) performances obtained with the developed tolerant catalysts, a classical Pt/C nanomaterial was used for comparison. Using 5 M methanol concentration in a situation where the fuel crossover is 100% (MRFC-mixed reactant fuel cell application), the maximum power density of the fuel cell with a Pt/C cathodic catalyst decreased by 80% in comparison with what is observed in the laminar flow fuel cell (LFFC) configuration. With Pt(x)Ti(y)/C and Pt(x)Se(y)/C cathode nanomaterials, the performance loss was only 55% and 20%, respectively. The evaluation of the tolerant cathode catalysts in an air-breathing microfluidic fuel cell suggests the development of a novel nanometric system that will not be size restricted. These interesting results are the consequence of the high methanol tolerance of these advanced electrocatalysts via surface electronic modification of Pt. Herein we used X-ray photoelectron and in situ FTIR spectroscopies to investigate the origin of the high methanol tolerance on modified Pt catalysts.

  15. Degradation Characteristics of Wood Using Supercritical Alcohols

    Directory of Open Access Journals (Sweden)

    Jeeban Poudel

    2012-11-01

    Full Text Available In this work, the characteristics of wood degradation using supercritical alcohols have been studied. Supercritical ethanol and supercritical methanol were used as solvents. The kinetics of wood degradation were analyzed using the nonisothermal weight loss technique with heating rates of 3.1, 9.8, and 14.5 °C/min for ethanol and 5.2, 11.3, and 16.3 °C/min for methanol. Three different kinetic analysis methods were implemented to obtain the apparent activation energy and the overall reaction order for wood degradation using supercritical alcohols. These were used to compare with previous data for supercritical methanol. From this work, the activation energies of wood degradation in supercritical ethanol were obtained as 78.0–86.0, 40.1–48.1, and 114 kJ/mol for the different kinetic analysis methods used in this work. The activation energies of wood degradation in supercritical ethanol were obtained as 78.0–86.0, 40.1–48.1, and 114 kJ/mol. This paper also includes the analysis of the liquid products obtained from this work. The characteristic analysis of liquid products on increasing reaction temperature and time has been performed by GC-MS. The liquid products were categorized according to carbon numbers and aromatic/aliphatic components. It was found that higher conversion in supercritical ethanol occurs at a lower temperature than that of supercritical methanol. The product analysis shows that the majority of products fall in the 2 to 15 carbon number range.

  16. Extraction of pesticides in soil using supercritical carbon dioxide co-solvents

    International Nuclear Information System (INIS)

    Forero, Jose R; Castro, Henry I; Guerrero, Jairo A.

    2009-01-01

    In this study, three organic solvents (ethyl acetate, methanol and acetone) were used as co solvent in supercritical fluid extraction (SFE) of a mixture of pesticides with different physical and chemical properties present in soil. These pesticides were determined by gas chromatography with electronic micro capture detector μECD and nitrogen-phosphorus detector (NPD), coupled in parallel. The extractions were performed on spiked soil samples using supercritical carbon dioxide (CO 2 SC) as the extracting phase to 35 celsius degrade and 14 MPa, using 10 mL of each co solvent and it was found that methanol offers the greatest efficiency in the extraction process obtaining recovery values between 51.24 and 123.50%.

  17. A process model to estimate the cost of industrial scale biodiesel production from waste cooking oil by supercritical transesterification

    NARCIS (Netherlands)

    Kasteren, van J.M.N.; Nisworo, A.P.

    2007-01-01

    This paper describes the conceptual design of a production process in which waste cooking oil is converted via supercritical transesterification with methanol to methyl esters (biodiesel). Since waste cooking oil contains water and free fatty acids, supercritical transesterification offers great

  18. Stable Organic Monolayers on Oxide-Free Silicon/Germanium in a Supercritical Medium: A New Route to Molecular Electronics.

    Science.gov (United States)

    Puniredd, Sreenivasa Reddy; Jayaraman, Sundaramurthy; Yeong, Sai Hooi; Troadec, Cedric; Srinivasan, M P

    2013-05-02

    Oxide-free Si and Ge surfaces have been passivated and modified with organic molecules by forming covalent bonds between the surfaces and reactive end groups of linear alkanes and aromatic species using single-step deposition in supercritical carbon dioxide (SCCO2). The process is suitable for large-scale manufacturing due to short processing times, simplicity, and high resistance to oxidation. It also allows the formation of monolayers with varying reactive terminal groups, thus enabling formation of nanostructures engineered at the molecular level. Ballistic electron emission microscopy (BEEM) spectra performed on the organic monolayer on oxide-free silicon capped by a thin gold layer reveals for the first time an increase in transmission of the ballistic current through the interface of up to three times compared to a control device, in contrast to similar studies reported in the literature suggestive of oxide-free passivation in SCCO2. The SCCO2 process combined with the preliminary BEEM results opens up new avenues for interface engineering, leading to molecular electronic devices.

  19. Velocity distribution of laser photoionized neutrals ejected from methanol-dosed aluminium(111) by electron-stimulated desorption

    International Nuclear Information System (INIS)

    Young, C.E.; Whitten, J.E.; Pellin, M.J.; Gruen, D.M.; Jones, P.L.; Ohio State Univ., Columbus, OH

    1989-01-01

    Nonresonant multiphoton ionization at 193 nm wavelength was employed for efficient detection of electron-stimulated neutral desorption from Al(111) dosed with methanol to produce monolayer methoxide coverage. Velocity spectra were measured by the flight time from the crystal surface to the focal region of the laser beam with a pulsed primary electron beam of 3 keV and the sample at 300 K. Either the C + or HCO + photofragment indicated the same non-Boltzmann velocity spectrum for the neutral parent precursor with a peak kinetic energy of ∼0.1 eV. Identical distributions were obtained when the cleaned crystal was pre-oxidized with O 2 prior to methanol dosing. As the crystal temperature was raised, photoion signal from the HCO + fragment declined steadily, while C + increased until ∼550 K. The total cross section for loss of parent signal with dose of 3 keV electrons was measured to be 2±1 x 10 -17 cm -2 . 19 refs., 4 figs

  20. Supercritical fluid extraction of reed (thypa)

    Energy Technology Data Exchange (ETDEWEB)

    Kucuk, M.; Genel, Y. [YYU Educational Faculty, Van (Turkey); Demir, H. [YYU Science and Art Faculty, Van (Turkey)

    2005-04-15

    Reed (typha) mill was converted to liquid products by using organic solvents (methanol, ethanol and acetone) with catalysts (% 10 NaOH and ZnCl{sub 2}) and without catalyst in an autoclave at temperatures of 533, 553, and 573 K. The liquid products were extracted by liquid-liquid extraction [DSA1] (benzene and diethyl ether). The yields from supercritical methanol, ethanol and acetone conversions were 36.2, 24.5, and 55.1%, respectively, at 573 K. In the catalytic runs with methanol and ethanol extracts were 46.3 and 35.5% (for NaOH catalyst) and 51.8 and 38.5% (for ZnCl{sub 2} catalyst) respectively, at 573 K. The yields from supercritical methanol were increased from 38.2 to 52.4% as the temperature was increased from 533 to 573 K in the catalytic run. (Author)

  1. Thermodynamic and Kinetic Requirements in Anaerobic Methane Oxidizing Consortia Exclude Hydrogen, Acetate, and Methanol as Possible Electron Shuttles.

    Science.gov (United States)

    Sørensen, K.B.; Finster, K.; Ramsing, N.B.

    2001-07-01

    Anaerobic methane oxidation (AMO) has long remained an enigma in microbial ecology. In the process the net reaction appears to be an oxidation of methane with sulfate as electron acceptor. In order to explain experimental data such as effects of inhibitors and isotopic signals in biomarkers it has been suggested that the process is carried out by a consortium of bacteria using an unknown compound to shuttle electrons between the participants. The overall change in free energy during AMO with sulfate is very small (?22 kJ mol-1) at in situ concentrations of methane and sulfate. In order to share the available free energy between the members of the consortium, the concentration of the intermediate electron shuttle compound becomes crucial. Diffusive flux of a substrate (i.e, the electron shuttle) between bacteria requires a stable concentration gradient where the concentration is higher in the producing organism than in the consuming organism. Since changes in concentrations cause changes in reaction free energies, the diffusive flux of a catabolic product/substrate between bacteria is associated with a net loss of available energy. This restricts maximal inter-bacterial distances in consortia composed of stationary bacteria. A simple theoretical model was used to describe the relationship between inter-bacterial distances and the energy lost due to concentration differences in consortia. Key parameters turned out to be the permissible concentration range of the electron shuttle in the consortium (i.e., the concentration range that allows both participants to gain sufficient energy) and the stoichiometry of the partial reactions. The model was applied to two known consortia degrading ethanol and butyrate and to four hypothetical methane-oxidizing consortia (MOC) based on interspecies transfer of hydrogen, methanol, acetate, or formate, respectively. In the first three MOCs the permissible distances between producers and consumers of the transferred compounds were

  2. Electron mobility in supercritical ethane as a function of density and temperature

    International Nuclear Information System (INIS)

    Nishikawa, M.; Holroyd, R.A.; Sowada, U.

    1980-01-01

    The electron mobility is reported for ethane as a function of density at various temperatures above T/sub c/. The high pressure cell used permits measurements to 200 atm. Our analysis shows that theory is consistent with the ethane mobility results at low and intermediate densities. At densities less than 1 x 10 21 molecules/cm 3 electrons are scattered by isolated ethane molecules and the Lorentz equation is valid. At intermediate densities, μ/sub e/ correlates with the square of the velocity of sound, indicating that in dense fluids the adiabatic compressibility must be included. The data are consistent with a modified Cohen--Lekner equation, and the minimum in μ/sub e/N observed at densities just below d/sub c/ is qualitatively accounted for by changes in the adiabatic compressibility. Thus the concept of quasilocalization, suggested by others to qualitatively explain such minima, is unnecessary here. At higher densities an additional, unspecified, scattering mechanism becomes important

  3. Evidence for CO formation in irradiated methanol and acetone: contribution of low-energy electron-energy-loss spectroscopy to γ-radiolysis

    International Nuclear Information System (INIS)

    Jay-Gerin, J.-P.; Fraser, M.-J.; Michaud, M.; Sanche, L.; Swiderek, P.; Ferradini, C.

    1997-01-01

    Energy-loss spectra for low-energy electrons incident on acetone condensed on a multilayer film of argon, and on a methanol film deposited on a metallic substrate, are reported. In both cases, the formation of carbon monoxide has been detected. These results are directly related to those obtained in the liquid-phase γ-radiolysis of the two compounds. (author)

  4. Methanol as electron donor for thermophilic biological sulfate and sulfite reduction

    NARCIS (Netherlands)

    Weijma, J.

    2000-01-01

    Sulfur oxyanions (e.g. sulfate, sulfite) can be removed from aqueous waste- and process streams by biological reduction with a suitable electron donor to sulfide, followed by partial chemical or biological oxidation of sulfide to elemental sulfur. The aim of the research described in this

  5. Direct Methanol Fuel Cell systems in portable electronics - a metrics-based conceptualization approach

    NARCIS (Netherlands)

    Flipsen, S.F.J.

    2010-01-01

    It is impossible to imagine life without portable electronics like the laptop computer and cell phone. All these products are powered by a battery, granting them grid independence and all-round protability. Connectivity to the internet and an increase of functionality demands for a better battery.

  6. Formation of salbutamol sulphate microparticles using solution enhanced dispersion by supercritical carbon dioxide

    Directory of Open Access Journals (Sweden)

    Abdolhossein Rouholamini Najafabadi

    2005-01-01

    Full Text Available Salbutamol sulphate (SS was precipitated by supercritical carbon dioxide (SC-CO2 using a homemade system at two different pressures. This process is characterized by spraying a methanolic solution of the drug into the supercritical fluid (SCF, extraction of the solvent by SC-CO2 and formation of drug particles. The morphology and size distribution of precipitated SS particles were characterized using scanning electron microscope and laser diffraction particle size analyzer respectively. FTIR spectra were used before and after processing to asses crystal modifications. Depending on the processing conditions, needle-like and flake-like particles with different size distributions were observed. The average size of the flake like particles was less than needle-like particles and the span parameter showed a narrower size distribution of the processed in comparison with the unprocessed materials. Analysis by FTIR showed that there was no significant effect on the structure of the drug under these processing conditions.

  7. Solvation of o-hydroxybenzoic acid in pure and modified supercritical carbon dioxide, according to numerical modeling data

    Science.gov (United States)

    Antipova, M. L.; Gurina, D. L.; Odintsova, E. G.; Petrenko, V. E.

    2015-08-01

    The dissolution of an elementary fragment of crystal structure (an o-hydroxybenzoic acid ( o-HBA) dimer) in both pure and modified supercritical (SC) carbon dioxide by adding methanol (molar fraction, 0.035) at T = 318 K, ρ = 0.7 g/cm3 is simulated. Features of the solvation mechanism in each solvent are revealed. The solvation of o-HBA in pure SC CO2 is shown to occur via electron donor-acceptor interactions. o-HBA forms a solvate complex in modified SC CO2 through hydrogen bonds between the carboxyl group and methanol. The hydroxyl group of o-HBA participates in the formation of an intramolecular hydrogen bond, and not in interactions with the solvent. It is concluded that the o-HBA-methanol complex is a stable molecular structure, and its lifetime is one order of magnitude higher than those of other hydrogen bonds in fluids.

  8. Measurement of polychlorinated biphenyls in solid waste such as transformer insulation paper by supercritical fluid extraction and gas chromatography electron capture detection.

    Science.gov (United States)

    Chikushi, Hiroaki; Fujii, Yuka; Toda, Kei

    2012-09-21

    In this work, a method for measuring polychlorinated biphenyls (PCBs) in contaminated solid waste was investigated. This waste includes paper that is used in electric transformers to insulate electric components. The PCBs in paper sample were extracted by supercritical fluid extraction and analyzed by gas chromatography-electron capture detection. The recoveries with this method (84-101%) were much higher than those with conventional water extraction (0.08-14%), and were comparable to those with conventional organic solvent extraction. Limit of detection was 0.0074 mg kg(-1) and measurable up to 2.5 mg kg(-1) for 0.5 g of paper sample. Data for real insulation paper by the proposed method agreed well with those by the conventional organic solvent extraction. Extraction from wood and concrete was also investigated and good performance was obtained as well as for paper samples. The supercritical fluid extraction is simpler, faster, and greener than conventional organic solvent extraction. Copyright © 2012 Elsevier B.V. All rights reserved.

  9. Probing electronic and vibrational properties at the electrochemical interface using SFG spectroscopy: Methanol electro-oxidation on Pt(1 1 0)

    Science.gov (United States)

    Vidal, F.; Busson, B.; Tadjeddine, A.

    2005-02-01

    We report the study of methanol electro-oxidation on Pt(1 1 0) using infrared-visible sum-frequency generation (SFG) vibrational spectroscopy. The use of this technique enables to probe the vibrational and electronic properties of the interface simultaneously in situ. We have investigated the vibrational properties of the interface in the CO ads internal stretch spectral region (1700-2150 cm -1) over a wide range of potentials. The analysis of the evolution of the C-O stretch line shape, which is related to the interference between the vibrational and electronic parts of the non-linear response, with the potential allows us to show that the onset of bulk methanol oxidation corresponds to the transition from a negatively to a positively charged surface.

  10. Highly water-dispersible, mixed ionic-electronic conducting, polymer acid-doped polyanilines as ionomers for direct methanol fuel cells.

    Science.gov (United States)

    Murthy, Arun; Manthiram, Arumugam

    2011-06-28

    Highly water-dispersible polymer acid-doped polyanilines have been synthesized and evaluated as an alternative for expensive Nafion ionomers in the anode of direct methanol fuel cells (DMFC). These polymers as ionomers lead to higher performance in single cell DMFC compared to Nafion ionomers due to mixed ionic-electronic conduction, water dispersibility, and co-catalytic activity. This journal is © The Royal Society of Chemistry 2011

  11. CeO2/rGO/Pt sandwich nanostructure: rGO-enhanced electron transmission between metal oxide and metal nanoparticles for anodic methanol oxidation of direct methanol fuel cells.

    Science.gov (United States)

    Yu, Xue; Kuai, Long; Geng, Baoyou

    2012-09-21

    Pt-based nanocomposites have been of great research interest. In this paper, we design an efficient MO/rGO/Pt sandwich nanostructure as an anodic electrocatalyst for DMFCs with combination of the merits of rigid structure of metallic oxides (MOs) and excellent electronic conductivity of reduced oxidized graphene (rGO) as well as overcoming their shortcomings. In this case, the CeO(2)/rGO/Pt sandwich nanostructure is successfully fabricated through a facile hydrothermal approach in the presence of graphene oxide and CeO(2) nanoparticles. This structure has a unique building architecture where rGO wraps up the CeO(2) nanoparticles and Pt nanoparticles are homogeneously dispersed on the surface of rGO. This novel structure endows this material with great electrocatalytic performance in methanol oxidation: it reduces the overpotential of methanol oxidation significantly and its electrocatalytic activity and stability are much enhanced compared with Pt/rGO, CeO(2)/Pt and Pt/C catalysts. This work supplies a unique MO/rGO/Pt sandwich nanostructure as an efficient way to improve the electrocatalytic performance, which will surely shed some light on the exploration of some novel structures of electrocatalyst for DMFCs.

  12. Electron Microscopic Analysis and Structural Characterization of Novel NADP(H)-Containing Methanol : N,N'-Dimethyl-4-Nitrosoaniline Oxidoreductases from the Gram-Positive Methylotrophic Bacteria Amycolatopsis methanolica and Mycobacterium gastri MB19

    NARCIS (Netherlands)

    Bystrykh, Leonid V.; Vonck, Janet; Bruggen, Ernst F.J. van; Beeumen, Jozef van; Samyn, Bart; Govorukhina, Natalya I.; Arfman, Nico; Duine, Johannis A.; Dijkhuizen, Lubbert

    The quaternary protein structure of two methanol:N,N'-dimethyl-4-nitrosoaniline (NDMA) oxidoreductases purified from Amycolatopsis methanolica and Mycobacterium gastri MB19 was analyzed by electron microscopy and image processing. The enzymes are decameric proteins (displaying fivefold symmetry)

  13. Functional separation of oxidation–reduction reactions and electron transport in PtRu/ND and conductive additive hybrid electrocatalysts during methanol oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Yan; Wang, Yanhui [State Key Laboratory of Metastable Materials Science and Technology, College of Materials Science and Engineering, Yanshan University, Qinhuangdao 066004 (China); Bian, Linyan [College of Physics and Chemistry, Henan Polytechnic University, Jiaozuo, Henan 454000 (China); Lu, Rui [State Key Laboratory of Metastable Materials Science and Technology, College of Materials Science and Engineering, Yanshan University, Qinhuangdao 066004 (China); Zang, Jianbing, E-mail: jbzang@ysu.edu.cn [State Key Laboratory of Metastable Materials Science and Technology, College of Materials Science and Engineering, Yanshan University, Qinhuangdao 066004 (China)

    2016-02-28

    Graphical abstract: - Highlights: • Functional separation of reactions and electron transport in PtRu/ND + AB (or CNT). • A conductive network was formed after the addition of AB or CNT. • PtRu/ND + AB (or CNT) exhibited enhanced activity and stability than PtRu/ND. - Abstract: Undoped nanodiamond (ND) supported PtRu (PtRu/ND) electrocatalyst for methanol oxidation reactions (MOR) in direct methanol fuel cells was prepared by a microwave-assisted polyol reduction method. Sp{sup 3}-bonded ND possesses high electrochemical stability but low conductivity, while sp{sup 2}-bonded carbon nanomaterials with high conductivity are prone to oxidation. Therefore, the functions of the supporting material were separated in this study. ND (sp{sup 3}), as a support, and AB or CNTs (sp{sup 2}), as a conductive additive, were combined to form the hybrid electrocatalysts PtRu/ND + AB and PtRu/ND + CNT for MOR. The morphology of the electrocatalysts was characterized by scanning electron microscopy and electrochemical measurements were performed using an electrochemical workstation. The results indicated that the electrocatalytic activity of PtRu/ND for MOR was improved with the addition of AB or CNTs as a conductive additive. Moreover, adding CNTs to PtRu/ND as a conductive additive showed better electrocatalytic activities than adding AB, which can be ascribed to the better electron-transfer ability of CNTs.

  14. Study by electron paramagnetic resonance of the radiolysis of pyridine N-oxide in a vitreous methanol matrix

    International Nuclear Information System (INIS)

    Quaegebeur, J.P.; Perly, B.

    1977-01-01

    The analysis of esr spectra derived from γ irradiated pyridine N-oxide in a methanolic vitreous matrix at 77 K shows the presence of a mixture of 2- and 4-azacyclohexadienyl N-oxide radicals formed by the addition of the hydroxymethyl primary species to the pyridine ring. The structure of the different radicals was determined by comparison with spectra derived from several substituted pyridine N-oxides

  15. Complete removal of uranyl nitrate from tissue matrix using supercritical fluid extraction

    International Nuclear Information System (INIS)

    Kumar, R.; Sivaraman, N.; Senthil Vadivu, E.; Srinivasan, T.G.; Vasudeva Rao, P.R.

    2003-01-01

    The removal of uranyl nitrate from tissue matrix has been studied with supercritical carbon dioxide modified with methanol alone as well as complexing reagents dissolved in methanol. A systematic study of various complexing agents led to the development of an extraction procedure for the quantitative recovery of uranium from tissue matrix with supercritical carbon dioxide modified with methanol containing small quantities of acetylacetone. The drying time and temperature employed in loading of uranyl nitrate onto tissue paper were found to influence the extraction efficiency significantly

  16. Quantum mechanics capacitance molecular mechanics modeling of core-electron binding energies of methanol and methyl nitrite on Ag(111) surface.

    Science.gov (United States)

    Löytynoja, T; Li, X; Jänkälä, K; Rinkevicius, Z; Ågren, H

    2016-07-14

    We study a newly devised quantum mechanics capacitance molecular mechanics (QMCMM) method for the calculation of core-electron binding energies in the case of molecules adsorbed on metal surfaces. This yet untested methodology is applied to systems with monolayer of methanol/methyl nitrite on an Ag(111) surface at 100 K temperature. It was found out that the studied C, N, and O 1s core-hole energies converge very slowly as a function of the radius of the metallic cluster, which was ascribed to build up of positive charge on the edge of the Ag slab. Further analysis revealed that an extrapolation process can be used to obtain binding energies that deviated less than 0.5 eV against experiments, except in the case of methanol O 1s where the difference was as large as 1.8 eV. Additional QM-cluster calculations suggest that the latter error can be connected to the lack of charge transfer over the QM-CMM boundary. Thus, the results indicate that the QMCMM and QM-cluster methods can complement each other in a holistic picture of molecule-adsorbate core-ionization studies, where all types of intermolecular interactions are considered.

  17. Diiodination of Alkynes in supercritical Carbon dioxide

    Institute of Scientific and Technical Information of China (English)

    李金恒; 谢叶香; 尹笃林; 江焕峰

    2003-01-01

    A general,green and efficient method for the synthesis of transdiiodoalkenes in CO2(sc) has been developed.Trans-diiodoalkenes were obtained stereospecifically in quantitative yields via diiodination of both electron-rich and electron-deficient alkynes in the presence of KI,Ce(SO4)2 and water in supercritical carbon dioxide [CO2(sc)]at 40℃.

  18. Radiolytic synthesis of carbon-supported PtRu nanoparticles using high-energy electron beam: effect of pH control on the PtRu mixing state and the methanol oxidation activity

    International Nuclear Information System (INIS)

    Ohkubo, Yuji; Kageyama, Satoru; Seino, Satoshi; Nakagawa, Takashi; Kugai, Junichiro; Nitani, Hiroaki; Ueno, Koji; Yamamoto, Takao A.

    2013-01-01

    Electrode catalysts composed of carbon-supported PtRu nanoparticles (PtRu/C) for use as a direct methanol fuel cell anode were synthesized by the reduction of precursor ions in an aqueous solution via irradiation with a high-energy electron beam. The effect of pH control in the precursor solution on the PtRu mixing state and the methanol oxidation activity was studied in order to enhance the catalytic activity for methanol oxidation. The PtRu/C structures were characterized by transmission electron microscopy, inductively coupled plasma atomic emission spectrometry, X-ray fluorescence spectrometry, and X-ray diffraction and X-ray absorption fine structure techniques. The methanol oxidation activity was evaluated by linear sweep voltammetry. The initial pH of the precursor solution has little influence on the average grain size for the metal particles (approximately 3.5 nm) on the carbon particle supports, but the dispersibility of the metal particles, PtRu mixing state, and methanol oxidation activity differed. The maintenance of a low pH in the precursor solution gave the best dispersibility of the PtRu nanoparticles supported on the surface of the carbon particles, whereas, a high pH gave the best PtRu mixing state and the highest oxidation current although a low dispersibility of the PtRu nanoparticles supported on the surface of the carbon particles was obtained. The PtRu mixing state strongly correlated with the methanol oxidation current. In addition, a high pH was more effective for PtRu mixing when using an electron beam irradiation reduction method, because the complexation reaction of the chelating agents was improved, which resulted in an enhancement of the catalytic activity for methanol oxidation.

  19. Radiolytic synthesis of carbon-supported PtRu nanoparticles using high-energy electron beam: effect of pH control on the PtRu mixing state and the methanol oxidation activity

    Energy Technology Data Exchange (ETDEWEB)

    Ohkubo, Yuji, E-mail: okubo@mit.eng.osaka-u.ac.jp; Kageyama, Satoru; Seino, Satoshi; Nakagawa, Takashi; Kugai, Junichiro [Osaka University, Graduate School of Engineering (Japan); Nitani, Hiroaki [High Energy Accelerator Research Organization (KEK), Institute of Materials Structure Science (Japan); Ueno, Koji [Japan Electron Beam Irradiation Service Ltd (Japan); Yamamoto, Takao A. [Osaka University, Graduate School of Engineering (Japan)

    2013-05-15

    Electrode catalysts composed of carbon-supported PtRu nanoparticles (PtRu/C) for use as a direct methanol fuel cell anode were synthesized by the reduction of precursor ions in an aqueous solution via irradiation with a high-energy electron beam. The effect of pH control in the precursor solution on the PtRu mixing state and the methanol oxidation activity was studied in order to enhance the catalytic activity for methanol oxidation. The PtRu/C structures were characterized by transmission electron microscopy, inductively coupled plasma atomic emission spectrometry, X-ray fluorescence spectrometry, and X-ray diffraction and X-ray absorption fine structure techniques. The methanol oxidation activity was evaluated by linear sweep voltammetry. The initial pH of the precursor solution has little influence on the average grain size for the metal particles (approximately 3.5 nm) on the carbon particle supports, but the dispersibility of the metal particles, PtRu mixing state, and methanol oxidation activity differed. The maintenance of a low pH in the precursor solution gave the best dispersibility of the PtRu nanoparticles supported on the surface of the carbon particles, whereas, a high pH gave the best PtRu mixing state and the highest oxidation current although a low dispersibility of the PtRu nanoparticles supported on the surface of the carbon particles was obtained. The PtRu mixing state strongly correlated with the methanol oxidation current. In addition, a high pH was more effective for PtRu mixing when using an electron beam irradiation reduction method, because the complexation reaction of the chelating agents was improved, which resulted in an enhancement of the catalytic activity for methanol oxidation.

  20. Extraction with supercritical gases

    Energy Technology Data Exchange (ETDEWEB)

    Schneider, G M; Wilke, G; Stahl, E

    1980-01-01

    The contents of this book derives from a symposium on the 5th and 6th of June 1978 in the ''Haus der Technik'' in Essen. Contributions were made to separation with supercritical gases, fluid extraction of hops, spices and tobacco, physicochemical principles of extraction, phase equilibria and critical curves of binary ammonia-hydrocarbon mixtures, a quick method for the microanalytical evaluation of the dissolving power of supercritical gases, chromatography with supercritical fluids, the separation of nonvolatile substances by means of compressed gases in countercurrent processes, large-scale industrial plant for extraction with supercritical gases, development and design of plant for high-pressure extraction of natural products.

  1. Petroleum Refinery Effluents Treatment by Advanced Oxidation Process with Methanol

    Energy Technology Data Exchange (ETDEWEB)

    Shoucheng, Wen [Yangtze Univ., HuBei Jingzhou (China)

    2014-02-15

    Petroleum refinery effluents are waste originating from industries primarily engaged in refining crude oil. It is a very complex compound of various oily wastes, water, heavy metals and so on. Conventional processes are unable to effectively remove the chemical oxygen demand (COD) of petroleum refinery effluents. Supercritical water oxidation (SCWO) was proposed to treat petroleum refinery effluents. In this paper, methanol was used to investigate co-oxidative effect of methanol on petroleum refinery effluents treatment. The results indicated that supercritical water oxidation is an effective process for petroleum refinery effluents treatment. Adding methanol caused an increase in COD removal. When reaction temperature is 440 .deg. C, residence time is 20 min, OE is 0.5 and initial COD is 40000 mg/L, and COD removal increases 8.5%.

  2. Petroleum Refinery Effluents Treatment by Advanced Oxidation Process with Methanol

    International Nuclear Information System (INIS)

    Shoucheng, Wen

    2014-01-01

    Petroleum refinery effluents are waste originating from industries primarily engaged in refining crude oil. It is a very complex compound of various oily wastes, water, heavy metals and so on. Conventional processes are unable to effectively remove the chemical oxygen demand (COD) of petroleum refinery effluents. Supercritical water oxidation (SCWO) was proposed to treat petroleum refinery effluents. In this paper, methanol was used to investigate co-oxidative effect of methanol on petroleum refinery effluents treatment. The results indicated that supercritical water oxidation is an effective process for petroleum refinery effluents treatment. Adding methanol caused an increase in COD removal. When reaction temperature is 440 .deg. C, residence time is 20 min, OE is 0.5 and initial COD is 40000 mg/L, and COD removal increases 8.5%

  3. Nano-composite of PtRu alloy electrocatalyst and electronically conducting polymer for use as the anode in a direct methanol fuel cell

    Energy Technology Data Exchange (ETDEWEB)

    Jongho Choi; Kyungwon Park; Hyekyung Lee; Youngmin Kim; Jaesuk Lee; Yungeun Sung [Kwangju Inst. of Science and Technology, Dept. of Materials Science and Engineering, Gwangju (Korea)

    2003-08-15

    Nano-composites comprised of PtRu alloy nanoparticles and an electronically conducting polymer for the anode electrode in direct methanol fuel cell (DMFC) were prepared. Two conducting polymers of poly(N-vinyl carbazole) and poly(9-(4-vinyl-phenyl)carbazole) were used for the nano-composite electrodes. Structural analyses were carried out using Fourier transform nuclear magnetic resonance spectroscopy, AC impedance spectroscopy, X-ray diffraction (XRD), and transmission electron microscopy (TEM). Electrocatalytic activities were investigated by voltammetry and chronoamperometry in a 2 M CH{sub 3}OH/{sub 0.5} M H{sub 2}SO{sub 4} solution and the data compared with a carbon-supported PtRu electrode. XRD patterns indicated good alloy formation and nano-composite formation was confirmed by TEM. Electrochemical measurements and DMFC unit-cell tests indicate that the nano-composites could be useful in a DMFC, but its performance would be slightly lower than that of a carbon-supported electrode. The interfacial property between the PtRu-polymer nano-composite anode and the polymer electrolyte was good, as evidenced by scanning electron microscopy. For better performance in a DMFC, a higher electric conductivity of the polymer and a lower catalyst loss are needed in nano-composite electrodes. (Author)

  4. 1995 world methanol conference

    International Nuclear Information System (INIS)

    Anon.

    1995-01-01

    The 20 papers contained in this volume deal with the global markets for methanol, the production of MTBE, integrating methanol production into a coal-to-SNG complex, production of methanol from natural gas, catalysts for methanol production from various synthesis gases, combined cycle power plants using methanol as fuel, and economics of the methanol industry. All papers have been processed for inclusion on the data base

  5. Effect of supercritical fluid density on nanoencapsulated drug particle size using the supercritical antisolvent method.

    Science.gov (United States)

    Kalani, Mahshid; Yunus, Robiah

    2012-01-01

    The reported work demonstrates and discusses the effect of supercritical fluid density (pressure and temperature of supercritical fluid carbon dioxide) on particle size and distribution using the supercritical antisolvent (SAS) method in the purpose of drug encapsulation. In this study, paracetamol was encapsulated inside L-polylactic acid, a semicrystalline polymer, with different process parameters, including pressure and temperature, using the SAS process. The morphology and particle size of the prepared nanoparticles were determined by scanning electron microscopy and transmission electron microscopy. The results revealed that increasing temperature enhanced mean particle size due to the plasticizing effect. Furthermore, increasing pressure enhanced molecular interaction and solubility; thus, particle size was reduced. Transmission electron microscopy images defined the internal structure of nanoparticles. Thermal characteristics of nanoparticles were also investigated via differential scanning calorimetry. Furthermore, X-ray diffraction pattern revealed the changes in crystallinity structure during the SAS process. In vitro drug release analysis determined the sustained release of paracetamol in over 4 weeks.

  6. Continuous production of biodiesel under supercritical methyl acetate conditions: Experimental investigation and kinetic model.

    Science.gov (United States)

    Farobie, Obie; Matsumura, Yukihiko

    2017-10-01

    In this study, biodiesel production by using supercritical methyl acetate in a continuous flow reactor was investigated for the first time. The aim of this study was to elucidate the reaction kinetics of biodiesel production by using supercritical methyl. Experiments were conducted at various reaction temperatures (300-400°C), residence times (5-30min), oil-to-methyl acetate molar ratio of 1:40, and a fixed pressure of 20MPa. Reaction kinetics of biodiesel production with supercritical methyl acetate was determined. Finally, biodiesel yield obtained from this method was compared to that obtained with supercritical methanol, ethanol, and MTBE (methyl tertiary-butyl ether). The results showed that biodiesel yield with supercritical methyl acetate increased with temperature and time. The developed kinetic model was found to fit the experimental data well. The reactivity of supercritical methyl acetate was the lowest, followed by that of supercritical MTBE, ethanol, and methanol, under the same conditions. Copyright © 2017. Published by Elsevier Ltd.

  7. Feasibility of ion-pair/supercritical fluid extraction of an ionic compound--pseudoephedrine hydrochloride.

    Science.gov (United States)

    Eckard, P R; Taylor, L T

    1997-02-01

    The supercritical fluid extraction (SFE) of an ionic compound, pseudoephedrine hydrochloride, from a spiked-sand surface was successfully demonstrated. The effect of carbon dioxide density (CO2), supercritical fluid composition (pure vs. methanol modified), and the addition of a commonly used reversed-phase liquid chromatographic ion-pairing reagent, 1-heptanesulfonic acid, sodium salt, on extraction efficiency was examined. The extraction recoveries of pseudoephedrine hydrochloride with the addition of the ion-pairing reagent from a spiked-sand surface were shown to be statistically greater than the extraction recoveries without the ion-pairing reagent with both pure and methanol-modified carbon dioxide.

  8. Electrochemistry in supercritical fluids

    Science.gov (United States)

    Branch, Jack A.; Bartlett, Philip N.

    2015-01-01

    A wide range of supercritical fluids (SCFs) have been studied as solvents for electrochemistry with carbon dioxide and hydrofluorocarbons (HFCs) being the most extensively studied. Recent advances have shown that it is possible to get well-resolved voltammetry in SCFs by suitable choice of the conditions and the electrolyte. In this review, we discuss the voltammetry obtained in these systems, studies of the double-layer capacitance, work on the electrodeposition of metals into high aspect ratio nanopores and the use of metallocenes as redox probes and standards in both supercritical carbon dioxide–acetonitrile and supercritical HFCs. PMID:26574527

  9. Supercritical Airfoil Coordinates

    Data.gov (United States)

    National Aeronautics and Space Administration — Rectangular Supercritical Wing (Ricketts) - design and measured locations are provided in an Excel file RSW_airfoil_coordinates_ricketts.xls . One sheet is with Non...

  10. using Supercritical Fluid Extraction

    African Journals Online (AJOL)

    Methods: Supercritical CO2 extraction technology was adopted in this experiment to study the process of extraction of volatile oil from Polygonatum odoratum while gas chromatograph-mass spectrometer ..... Saponin rich fractions from.

  11. Evaluation of an amide-based stationary phase for supercritical fluid chromatography

    Science.gov (United States)

    Borges-Muñoz, Amaris C.; Colón, Luis A.

    2017-01-01

    A relatively new stationary phase containing a polar group embedded in a hydrophobic backbone (i.e., ACE® C18-amide) was evaluated for use in supercritical fluid chromatography. The amide-based column was compared with columns packed with bare silica, C18 silica, and a terminal-amide silica phase. The system was held at supercritical pressure and temperature with a mobile phase composition of CO2 and methanol as cosolvent. The linear solvation energy relationship model was used to evaluate the behavior of these stationary phases, relating the retention factor of selected probes to specific chromatographic interactions. A five-component test mixture, consisting of a group of drug-like molecules was separated isocratically. The results show that the C18-amide stationary phase provided a combination of interactions contributing to the retention of the probe compounds. The hydrophobic interactions are favorable; however, the electron donating ability of the embedded amide group shows a large positive interaction. Under the chromatographic conditions used, the C18-amide column was able to provide baseline resolution of all the drug-like probe compounds in a text mixture, while the other columns tested did not. PMID:27396487

  12. Supercritical fluid chromatography

    Science.gov (United States)

    Vigdergauz, M. S.; Lobachev, A. L.; Lobacheva, I. V.; Platonov, I. A.

    1992-03-01

    The characteristic features of supercritical fluid chromatography (SCFC) are examined and there is a brief historical note concerning the development of the method. Information concerning the use of supercritical fluid chromatography in the analysis of objects of different nature is presented in the form of a table. The roles of the mobile and stationary phases in the separation process and the characteristic features of the apparatus and of the use of the method in physicochemical research are discussed. The bibliography includes 364 references.

  13. Methanol adsorption on Pt(111)

    International Nuclear Information System (INIS)

    Melo, A.V.; Chottiner, G.S.; Hoffman, R.W.; O'Grady, W.E.

    1984-12-01

    High resolution electron energy loss spectroscopy has been used to study the decomposition of methanol on a Pt(111) surface. Several intermediate states in the decomposition are identified by quenching the sample when reactions occur. At 100 K a set of peaks at 800, 1040, 1350, and 2890 cm -1 indicates the presence of a multilayer molecularly adsorbed methanol. As the sample is warmed to 130 K peaks develop at 1700 and 2780 cm -1 , suggesting the formation of formaldehyde on the surface. With further heating, peaks grow at 1820 and 2560 cm -1 due to the formation of a formyl species during the decomposition of methanol over Pt(111). Further heating leads to the final conversion of the surface species to adsorbed CO and carbonaceous residues

  14. Selection of inactivation medium for fungal spores in clinical wastes by supercritical carbon dioxide.

    Science.gov (United States)

    Noman, Efaq; Norulaini Nik Ab Rahman, Nik; Al-Gheethi, Adel; Nagao, Hideyuki; Talip, Balkis A; Ab Kadir, Omar

    2018-05-21

    The present study aimed to select the best medium for inactivation of Aspergillus fumigatus, Aspergillus spp. in section Nigri, A. niger, A. terreus var. terreus, A. tubingensis, Penicillium waksmanii, P. simplicissimum, and Aspergillus sp. strain no. 145 spores in clinical wastes by using supercritical carbon dioxide (SC-CO 2 ). There were three types of solutions used including normal saline, seawater, distilled water, and physiological saline with 1% of methanol; each solution was tested at 5, 10, and 20 mL of the water contents. The experiments were conducted at the optimum operating parameters of supercritical carbon dioxide (30 MPa, 75 °C, 90 min). The results showed that the inactivation rate was more effective in distilled water with the presence of 1% methanol (6 log reductions). Meanwhile, the seawater decreases inactivation rate more than normal saline (4.5 vs. 5.1 log reduction). On the other hand, the experiments performed with different volumes of distilled water (5, 10, and 20 mL) indicated that A. niger spores were completely inactivated with 10 mL of distilled water. The inactivation rate of fungal spores decreased from 6 to 4.5 log as the amount of distilled water increased from 10 to 20 mL. The analysis for the spore morphology of A. fumigatus and Aspergillus spp. in section Nigri using scanning electron microscopy (SEM) has revealed the role of temperature and pressure in the SC-CO 2 in the destruction of the cell walls of the spores. It can be concluded that the distilled water represent the best medium for inactivation of fungal spores in the clinical solid wastes by SC-CO 2 .

  15. Processing behaviors of thin-film pentacene and benzene-1,4-diboronic acid in supercritical carbon dioxide

    International Nuclear Information System (INIS)

    Ngo, Truc T.; Keegan, James E.; George, Robert D.

    2011-01-01

    This research investigates the feasibility of using supercritical carbon dioxide (scCO 2 ) as a green solvent for processing organic thin film semiconductor, such as pentacene, and a potential molecular modifier for use in electronic device applications. Benzene-1,4-diboronic acid (BDBA) was selected as a molecular modifier in this work due to its electron deficient nature, which can potentially enhance pentacene's physical, chemical or electronic properties by changing its structure in the solid state. In this study, the solubilities of BDBA and pentacene in scCO 2 are measured as individual compounds and as co-solutes, at 313 K, using ultraviolet (UV) spectroscopy. Methanol co-solvent effects on solubility have also been characterized for each compound. The results show that BDBA is insoluble in pure scCO 2 up to 1.82 × 10 7 Pa. However, with a small amount of methanol added to the mixture, BDBA becomes soluble in solution with a solubility of 3.81 × 10 −4 mol/l at 9.00 × 10 6 -Pa-pressure. In contrast, pentacene is only soluble in scCO 2 at pressures above 1.10 × 10 7 Pa, and its solubility is decreased upon addition of methanol due to the non-polar nature of pentacene. When a pentacene thin film is treated with BDBA in scCO 2 /methanol solution, BDBA sorption is observed at pressures as low as 8.80 × 10 6 Pa. Based on these results, it is concluded that treatment of pentacene thin films in scCO 2 is a promising approach that can be optimized for BDBA and other similar molecular modifiers, to produce multi-component organic thin film devices.

  16. Process for obtaining methanol. Verfahren zur Gewinnung von Methanol

    Energy Technology Data Exchange (ETDEWEB)

    Link, H; Watson, A

    1983-12-08

    Synthetic gas is generated and converted to methanol in a reactor. After the separation of the crude methanol, there is a multi-stage methanol distillation. Condensate occurring during distillation is at least partly fed back before the methanol synthesis.

  17. Selective extraction of hydrocarbons, phosphonates and phosphonic acids from soils by successive supercritical fluid and pressurized liquid extractions.

    Science.gov (United States)

    Chaudot, X; Tambuté, A; Caude, M

    2000-01-14

    Hydrocarbons, dialkyl alkylphosphonates and alkyl alkylphosphonic acids are selectively extracted from spiked soils by successive implementation of supercritical carbon dioxide, supercritical methanol-modified carbon dioxide and pressurized water. More than 95% of hydrocarbons are extracted during the first step (pure supercritical carbon dioxide extraction) whereas no organophosphorus compound is evidenced in this first extract. A quantitative extraction of phosphonates is achieved during the second step (methanol-modified supercritical carbon dioxide extraction). Polar phosphonic acids are extracted during a third step (pressurized water extraction) and analyzed by gas chromatography under methylated derivatives (diazomethane derivatization). Global recoveries for these compounds are close to 80%, a loss of about 20% occurring during the derivatization process (co-evaporation with solvent). The developed selective extraction method was successfully applied to a soil sample during an international collaborative exercise.

  18. Methanol Fuel Cell

    Science.gov (United States)

    Voecks, G. E.

    1985-01-01

    In proposed fuel-cell system, methanol converted to hydrogen in two places. External fuel processor converts only part of methanol. Remaining methanol converted in fuel cell itself, in reaction at anode. As result, size of fuel processor reduced, system efficiency increased, and cost lowered.

  19. Capabilities and Limitations of an Association Theory for Chemicals in Liquid or Supercritical Solvents

    DEFF Research Database (Denmark)

    Tsivintzelis, Ioannis; Kontogeorgis, Georgios

    2012-01-01

    . The capabilities of the model are illustrated in the first two case studies: the phase behavior of mixtures used in the oxidation of 2-octanol in supercritical CO2 and the investigation of systems containing acetone, methanol, water, chloroform, and methyl acetate. In each case, both correlations of vapor...

  20. Supercritical fluid extraction of uranium from tissue paper matrix using organic extractants

    International Nuclear Information System (INIS)

    Kanekar, A.S.; Bhattacharyya, A.; Pathak, P.N.; Mohapatra, P.K.; Manchanda, V.K.

    2009-01-01

    Direct extraction of dried uranyl nitrate from tissue paper matrix was carried out using supercritical carbon dioxide modified with methanol solutions of extractants such as tri-n-butyl phosphate (TBP) and di-n-hexyl octanamide (DHOA)). The effects of temperature, pressure, extractant and nitric acid concentration on the extraction of uranyl ion were investigated. (author)

  1. Extraction of polycyclic aromatic hydrocarbons from polluted soils with binary and ternary supercritical phases

    International Nuclear Information System (INIS)

    Hollender, J.; Shneine, J.; Dott, W.; Heinzel, M.; Hagemann, H.W.; Gotz, G.K.E.

    1997-01-01

    The paper describes how supercritical fluid extractions (SFE) using carbon dioxide and modifiers (n-hexane, cyclohexane, toluene, methyl tert-butyl ether, methoxybenzene, dichloromethane, propanone, pyridine, methanol) as well as modifier mixtures (methanol-containing diethylamide, 2-aminoethan-1-ol, acetic acid) were performed to extract polycyclic aromatic hydrocarbons (PAHs) from real environmental samples polluted to a minor extent by mineral oil products and highly contaminated by brown coal tar. Comparing the results with those from Soxhlet extraction utilizing dichloromethane and SFE using pure carbon dioxide show that acidic or basic co-solvents give the highest PAH yields. Extraction efficiency decreases with reduced polarity of the modifier used and increases at higher concentrations of co-solvent. To explain the SFE results, several mechanisms of disruption of matrix-PAH interactions are considered: the competition between the modifier molecules and the active sites of soil's organic and inorganic matter to interact with non-covalent bondings to the analytes; and the splitting of electron donor-acceptor complexes between humic substances and PAHs induced by Lewis acids or Lewis bases

  2. Materials processing using supercritical fluids

    Directory of Open Access Journals (Sweden)

    Orlović Aleksandar M.

    2005-01-01

    Full Text Available One of the most interesting areas of supercritical fluids applications is the processing of novel materials. These new materials are designed to meet specific requirements and to make possible new applications in Pharmaceuticals design, heterogeneous catalysis, micro- and nano-particles with unique structures, special insulating materials, super capacitors and other special technical materials. Two distinct possibilities to apply supercritical fluids in processing of materials: synthesis of materials in supercritical fluid environment and/or further processing of already obtained materials with the help of supercritical fluids. By adjusting synthesis parameters the properties of supercritical fluids can be significantly altered which further results in the materials with different structures. Unique materials can be also obtained by conducting synthesis in quite specific environments like reversed micelles. This paper is mainly devoted to processing of previously synthesized materials which are further processed using supercritical fluids. Several new methods have been developed to produce micro- and nano-particles with the use of supercritical fluids. The following methods: rapid expansion of supercritical solutions (RESS supercritical anti-solvent (SAS, materials synthesis under supercritical conditions and encapsulation and coating using supercritical fluids were recently developed.

  3. Supercritical Synthesis of Biodiesel

    Directory of Open Access Journals (Sweden)

    Michel Vaultier

    2012-07-01

    Full Text Available The synthesis of biodiesel fuel from lipids (vegetable oils and animal fats has gained in importance as a possible source of renewable non-fossil energy in an attempt to reduce our dependence on petroleum-based fuels. The catalytic processes commonly used for the production of biodiesel fuel present a series of limitations and drawbacks, among them the high energy consumption required for complex purification operations and undesirable side reactions. Supercritical fluid (SCF technologies offer an interesting alternative to conventional processes for preparing biodiesel. This review highlights the advances, advantages, drawbacks and new tendencies involved in the use of supercritical fluids (SCFs for biodiesel synthesis.

  4. Supercritical fluid analytical methods

    International Nuclear Information System (INIS)

    Smith, R.D.; Kalinoski, H.T.; Wright, B.W.; Udseth, H.R.

    1988-01-01

    Supercritical fluids are providing the basis for new and improved methods across a range of analytical technologies. New methods are being developed to allow the detection and measurement of compounds that are incompatible with conventional analytical methodologies. Characterization of process and effluent streams for synfuel plants requires instruments capable of detecting and measuring high-molecular-weight compounds, polar compounds, or other materials that are generally difficult to analyze. The purpose of this program is to develop and apply new supercritical fluid techniques for extraction, separation, and analysis. These new technologies will be applied to previously intractable synfuel process materials and to complex mixtures resulting from their interaction with environmental and biological systems

  5. Electrocatalytic oxidation of methanol by the [Ru3O(OAc6(py2(CH3OH]3+cluster: improving the metal-ligand electron transfer by accessing the higher oxidation states of a multicentered system

    Directory of Open Access Journals (Sweden)

    Henrique E. Toma

    2010-01-01

    Full Text Available The [Ru3O(Ac6(py2(CH3OH]+ cluster provides an effective electrocatalytic species for the oxidation of methanol under mild conditions. This complex exhibits characteristic electrochemical waves at -1.02, 0.15 and 1.18 V, associated with the Ru3III,II,II/Ru3III,III,II/Ru 3III,III,III /Ru3IV,III,III successive redox couples, respectively. Above 1.7 V, formation of two RuIV centers enhances the 2-electron oxidation of the methanol ligand yielding formaldehyde, in agreement with the theoretical evolution of the HOMO levels as a function of the oxidation states. This work illustrates an important strategy to improve the efficiency of the oxidation catalysis, by using a multicentered redox catalyst and accessing its multiple higher oxidation states.

  6. Synthesis of biodiesel from soybean oil by coupling catalysis with subcritical methanol

    International Nuclear Information System (INIS)

    Yin Jianzhong; Xiao Min; Wang Aiqin; Xiu Zhilong

    2008-01-01

    Biodiesel synthesis from soybean oil and methanol was investigated under supercritical and subcritical conditions. Under the supercritical conditions, the maximum methyl ester yield exceeded 98% when the molar ratio of methanol to oil was 42:1 and the reaction temperature ranged from 260 deg. C to 350 deg. C. In order to decrease the operational temperature and pressures and to increase the conversion efficiency of methanol, first co-solvent was added to the reaction mixture to improve the reaction process, and then a novel idea was presented in which catalysis and supercritical effect were coupled together. Thus, with 2.5 wt% hexane, temperature of 300 deg. C, methanol to oil ratio of 42, a 85.5% conversion is observed in 30 min, while a 62.2% conversion is observed without hexane in the same condition; with less carbon dioxide, temperature of 300 deg. C, methanol to oil ratio of 42, a 91.6% conversion is observed in 20 min, while a 51.4% conversion is observed without carbon dioxide in the same condition; With only a little amount of potassium hydroxide as the catalyst (KOH/oil = 0.1 wt%), a 98% yield of methyl esters was obtained in 10 min at a reaction temperature of 160 deg. C and the molar ratio (methanol/oil) of 24:1. In contrast, above 1 wt% of catalyst is required in the conventional alkali-catalyzed method; while only 6% yield of methyl ester was obtained at 260 deg. C (corresponding to subcritical conditions) without the catalyst. This result demonstrated that by coupling the catalysis and subcritical operation, the amount of catalyst could be largely reduced and the methanol utilization could be significantly enhanced. Thus, the present method offers some advantages over both the conventional alkali-catalyst method and the expensive supercritical method

  7. Supercritical Water Reactors

    International Nuclear Information System (INIS)

    Bouchter, J.C.; Dufour, P.; Guidez, J.; Latge, C.; Renault, C.; Rimpault, G.

    2014-01-01

    The supercritical water reactor (SCWR) is one of the 6 concepts selected for the 4. generation of nuclear reactors. SCWR is a new concept, it is an attempt to optimize boiling water reactors by using the main advantages of supercritical water: only liquid phase and a high calorific capacity. The SCWR requires very high temperatures (over 375 C degrees) and very high pressures (over 22.1 MPa) to operate which allows a high conversion yield (44% instead of 33% for a PWR). Low volumes of coolant are necessary which makes the neutron spectrum shift towards higher energies and it is then possible to consider fast reactors operating with supercritical water. The main drawbacks of supercritical water is the necessity to use very high pressures which has important constraints on the reactor design, its physical properties (density, calorific capacity) that vary strongly with temperatures and pressures and its very high corrosiveness. The feasibility of the concept is not yet assured in terms of adequate materials that resist to corrosion, reactor stability, reactor safety, and reactor behaviour in accidental situations. (A.C.)

  8. Supercritical transitiometry of polymers.

    Science.gov (United States)

    Randzio, S L; Grolier, J P

    1998-06-01

    Employing supercritical fluids (SCFs) during polymers processing allows the unusual properties of SCFs to be exploited for making polymer products that cannot be obtained by other means. A new supercritical transitiometer has been constructed to permit study of the interactions of SCFs with polymers during processing under well-defined conditions of temperature and pressure. The supercritical transitiometer allows pressure to be exerted by either a supercritical fluid or a neutral medium and enables simultaneous determination of four basic parameters of a transition, i.e., p, T, Δ(tr)H and Δ(tr)V. This permits determination of the SCF effect on modification of the polymer structure at a given pressure and temperature and defines conditions to allow reproducible preparation of new polymer structures. Study of a semicrystalline polyethylene by this method has defined conditions for preparation of new microfoamed phases with good mechanical properties. The low densities and microporous structures of the new materials may make them useful for applications in medicine, pharmacy, or the food industry, for example.

  9. Technoeconomic study of supercritical biodiesel production plant

    International Nuclear Information System (INIS)

    Marchetti, J.M.; Errazu, A.F.

    2008-01-01

    Over the last years, biodiesel has gained more market due to its benefits and because it appears as the natural substitute for diesel. However, the highest cost of this process is associated with the raw material employed, making it a less competitive and more expensive fuel. Therefore, research is being done in order to use low price raw material, such as acid oils, frying oils or soapstocks. In this work, a biodiesel production plant was developed using supercritical methanol and acid oils as raw materials. This technology was compared with some other alternatives previously described with the aim of making a comparative study, not only on the technical aspects but also on the economic results. A process simulator was employed to produce the conceptual design and simulate each technology. Using these models, it was possible to analyze different scenarios and to evaluate productivity, raw material consumption, economic competitiveness and environmental impacts of each process. Although the supercritical alternative appears as a good technical possibility to produce biodiesel, today, it is not an economic alternative due to its high operating costs

  10. Kinetics and mechanism of methane oxidation in supercritical water

    International Nuclear Information System (INIS)

    Rofer, C.K.; Streit, G.E.

    1988-10-01

    This project, is a Hazardous Waste Remedial Actions Program (HAZWRAP) Research and Development task being carried out by the Los Alamos National Laboratory. Its objective is to achieve an understanding of the technology for use in scaling up and applying oxidation in supercritical water as a viable process for treating a variety of Department of Energy Defense Programs (DOE-DP) waste streams. This report presents experimental results for the kinetics of the oxidation of methane and methanol in supercritical water and computer modeling results for the oxidation of carbonmonoxide and methane in supercritical water. The experimental and modeling results obtained to date on these one-carbon model compounds indicate that the mechanism of oxidation in supercritical water can be represented by free-radical reactions with appropriate modifications for high pressure and the high water concentration. If these current trends are sustained, a large body of existing literature data on the kinetics of elementary reactions can be utilized to predict the behavior of other compounds and their mixtures. 7 refs., 4 figs., 3 tabs

  11. The Methanol Economy Project

    Energy Technology Data Exchange (ETDEWEB)

    Olah, George [Univ. of Southern California, Los Angeles, CA (United States); Prakash, G. K. [Univ. of Southern California, Los Angeles, CA (United States)

    2014-02-01

    The Methanol Economy Project is based on the concept of replacing fossil fuels with methanol generated either from renewable resources or abundant natural (shale) gas. The full methanol cycle was investigated in this project, from production of methanol through bromination of methane, bireforming of methane to syngas, CO2 capture using supported amines, co-electrolysis of CO2 and water to formate and syngas, decomposition of formate to CO2 and H2, and use of formic acid in a direct formic acid fuel cell. Each of these projects achieved milestones and provided new insights into their respective fields.

  12. Oxidation kinetics of model compounds of metabolic waste in supercritical water

    Science.gov (United States)

    Webley, Paul A.; Holgate, Henry R.; Stevenson, David M.; Tester, Jefferson W.

    1990-01-01

    In this NASA-funded study, the oxidation kinetics of methanol and ammonia in supercritical water have been experimentally determined in an isothermal plug flow reactor. Theoretical studies have also been carried out to characterize key reaction pathways. Methanol oxidation rates were found to be proportional to the first power of methanol concentration and independent of oxygen concentration and were highly activated with an activation energy of approximately 98 kcal/mole over the temperature range 480 to 540 C at 246 bar. The oxidation of ammonia was found to be catalytic with an activation energy of 38 kcal/mole over temperatures ranging from 640 to 700 C. An elementary reaction model for methanol oxidation was applied after correction for the effect of high pressure on the rate constants. The conversion of methanol predicted by the model was in good agreement with experimental data.

  13. Supercritical fluids processing: emerging opportunities

    International Nuclear Information System (INIS)

    Kovaly, K.A.

    1985-01-01

    This publication on the emerging opportunities of supercritical fluids processing reveals the latest research findings and development trends in this field. These findings and development trends are highlighted, and the results of applications of technology to the business of supercritical fluids are reported. Applications of supercritical fluids to chemical intermediates, environmental applications, chemical reactions, food and biochemistry processing, and fuels processing are discussed in some detail

  14. Catalytic methanol dissociation

    International Nuclear Information System (INIS)

    Alcinikov, Y.; Fainberg, V.; Garbar, A.; Gutman, M.; Hetsroni, G.; Shindler, Y.; Tatrtakovsky, L.; Zvirin, Y.

    1998-01-01

    Results of the methanol dissociation study on copper/potassium catalyst with alumina support at various temperatures are presented. The following gaseous and liquid products at. The catalytic methanol dissociation is obtained: hydrogen, carbon monoxide, carbon dioxide, methane, and dimethyl ether. Formation rates of these products are discussed. Activation energies of corresponding reactions are calculated

  15. Methanol fuel update

    International Nuclear Information System (INIS)

    Colledge, R.; Spacek, J.

    1992-01-01

    An overview is presented of methanol fuel developments, with particular reference to infrastructure, supply and marketing. Methanol offers reduced emissions, easy handling, is cost effective, can be produced from natural gas, coal, wood, or municipal waste, is a high performance fuel, is safer than gasoline, and contributes to energy security. Methanol supply, environmental benefits, safety/health issues, economics, passenger car economics, status of passenger car technology, buses, methanol and the prosperity initiative, challenges to implementation, and the role of government and original equipment manufacturers are discussed. Governments must assist in the provision of methanol refuelling infrastructure, and in providing an encouraging regulatory atmosphere. Discriminatory and inequitable taxing methods must be addressed, and an air quality agenda must be defined to allow the alternative fuel industry to respond in a timely manner

  16. Industrial applications and current trends in supercritical fluid technologies

    Directory of Open Access Journals (Sweden)

    Gamse Thomas

    2005-01-01

    Full Text Available Supercritical fluids have a great potential for wide fields of processes Although CO2 is still one of the most used supercritical gases, for special purposes propane or even fluorinated-chlorinated fluids have also been tested. The specific characteristics of supercritical fluids behaviour were analyzed such as for example the solubilities of different components and the phase equilibria between the solute and solvent. The application at industrial scale (decaffeinating of tea and coffee, hop extraction or removal of pesticides from rice, activity in supercritical extraction producing total extract from the raw material or different fractions by using the fractionated separation of beverages (rum, cognac, whisky, wine, beer cider, of citrus oils and of lipids (fish oils, tall oil were also discussed. The main interest is still for the extraction of natural raw materials producing food ingredients, nutraceuticals and phytopharmaceuticals but also cleaning purposes were tested such as the decontamination of soils the removal of residual solvents from pharmaceutical products, the extraction of flame retardants from electronic waste or precision degreasing and cleaning of mechanical and electronic parts. An increasing interest obviously exists for impregnation purposes based on supercritical fluids behaviour, as well as for the dying of fibres and textiles. The production of fine particles in the micron and submicron range, mainly for pharmaceutical products is another important application of supercritical fluids. Completely new products can be produced which is not possible under normal conditions. Supercritical fluid technology has always had to compete with the widespread opinion that these processes are very expensive due to very high investment costs in comparison with classical low-pressure equipment. Thus the opinion is that these processes should be restricted to high-added value products. A cost estimation for different plant sizes and

  17. Qualitative Analysis of Transesterification of Waste Pig Fat in Supercritical Alcohols

    Directory of Open Access Journals (Sweden)

    Jeeban Poudel

    2017-02-01

    Full Text Available In this work, the characteristics of waste pig fat degradation using supercritical alcohols have been studied. Comparative analysis of the influence of supercritical methanol and supercritical ethanol as solvents on the transesterification was the primary focus of this research. The experiments were carried out with waste pig fat to alcohol weight ratios of 1:1.5 (molar ratio: 1:40.5 for methanol and 1:28 for ethanol, 1:2.0 (molar ratio: 1:54 for methanol and 1:37.5 for ethanol and 1:2.5 (molar ratio: 1:67.5 for methanol and 1:47 for ethanol at transesterification temperatures 250, 270 and 290 °C for holding time 0, 15, 30, 45 and 60 min. Increase in the transesterification and holding time increased the conversion while increase in alcohol amount from 1:1.5 to 1:2.0 and 1:2.5 had minimal effect on the conversion. Further, majority of the ester composition in using SCM as solvent falls in the carbon range of C17:0, C19:1 and C19:2 while that for SCE falls in the carbon range of C18:0, C20:1 and C20:2. Glycerol was only present while using SCM as solvent.

  18. Dietary methanol and autism.

    Science.gov (United States)

    Walton, Ralph G; Monte, Woodrow C

    2015-10-01

    The authors sought to establish whether maternal dietary methanol during pregnancy was a factor in the etiology of autism spectrum disorders. A seven item questionnaire was given to women who had given birth to at least one child after 1984. The subjects were solicited from a large primary care practice and several internet sites and separated into two groups - mothers who had given birth to a child with autism and those who had not. Average weekly methanol consumption was calculated based on questionnaire responses. 550 questionnaires were completed by women who gave birth to a non-autistic child. On average these women consumed 66.71mg. of methanol weekly. 161 questionnaires were completed by women who had given birth to an autistic child. The average estimated weekly methanol consumption for this group was 142.31mg. Based on the results of the Wilcoxon rank sum-test, we see a significant difference between the reported methanol consumption rates of the two groups. This study suggests that women who have given birth to an autistic child are likely to have had higher intake of dietary sources of methanol than women who have not. Further investigation of a possible link of dietary methanol to autism is clearly warranted. Copyright © 2015 The Authors. Published by Elsevier Ltd.. All rights reserved.

  19. Supercritical fluids in ionic liquids

    NARCIS (Netherlands)

    Kroon, M.C.; Peters, C.J.; Plechkova, N.V.; Seddon, K.R.

    2014-01-01

    Ionic liquids and supercritical fluids are both alternative environmentally benign solvents, but their properties are very different. Ionic liquids are non-volatile but often considered highly polar compounds, whereas supercritical fluids are non-polar but highly volatile compounds. The combination

  20. Catalytic upgrading of sugar fractions from pyrolysis oils in supercritical mono-alcohols over Cu doped porous metal oxide

    NARCIS (Netherlands)

    Yin, Wang; Venderbosch, Hendrikus; Bottari, Giovanni; Krawzcyk, Krzysztof K.; Barta, Katalin; Heeres, Hero Jan

    In this work, we report on the catalytic valorization of sugar fractions, obtained by aqueous phase extraction of fast pyrolysis oils, in supercritical methanol (scMeOH) and ethanol (scEtOH) over a copper doped porous metal oxide (Cu-PMO). The product mixtures obtained are, in principle, suitable

  1. Extraction of Genistein from Sophora flavescens with Supercritical Carbon Dioxide

    Energy Technology Data Exchange (ETDEWEB)

    Han, Chang-Nam; Kang, Choon-Hyoung [Chonnam National University, Gwangju (Korea, Republic of)

    2015-08-15

    This study was directed to finding an optimum extraction condition of genistein from the S. flavescens with supercritical carbon dioxide as a solvent. In this effort, effects of the extraction conditions including pressure, temperature and a co-solvent on the extraction efficiency were investigated. The aqueous ethanol and methanol solutions were used as co-solvents while the tested operating pressure and temperature ranges were from 200 bar to 300 bar and from 308.15 K to 323.15 K, respectively. The concentration of genistein was determined by means of HPLC equipped with a UV detector. From the results, it was observed that an increase in pressure led to the higher extraction efficiency. Further, methanol showed better performance as a co-solvent than ethanol. The DPPH radical scavenging activities were measured to compare antioxidant activities of S. flavescens extracts.

  2. Real-time observation of the dehydrogenation processes of methanol on clean Ru(001) and Ru(001)-p(2×2) O surfaces by a temperature-programmed electron-stimulated desorption ion angular distribution/time-of-flight system

    Science.gov (United States)

    Sasaki, Takehiko; Itai, Yuichiro; Iwasawa, Yasuhiro

    1999-12-01

    Decomposition processes of methanol on clean and oxygen-precovered Ru(001) surfaces have been visualized in real time with a temperature-programmed (TP) electron-stimulated desorption ion angular distribution (ESDIAD)/time-of-flight (TOF) system. The mass of desorbed ions during temperature-programmed surface processes was identified by TOF measurements. In the case of methanol (CH 3OD) adsorption on Ru(001)-p(2×2)-O, a halo pattern of H + from the methyl group of methoxy species was observed at 100-200 K, followed by a broad pattern from the methyl group at 230-250 K and by a near-center pattern from O + ions originating from adsorbed CO above 300 K. The halo pattern is attributed to a perpendicular conformation of the CO bond axis of the methoxy species, leading to off-normal CH bond scission. On the other hand, methanol adsorbed on clean Ru(001) did not give any halo pattern but a broad pattern was observed along the surface normal, indicating that the conformation of the methoxy species is not ordered on the clean surface. Comparison between the ESDIAD images of the oxygen-precovered surface and the clean surface suggests that the precovered oxygen adatoms induce ordering of the methoxy species. Real-time ESDIAD measurements revealed that the oxygen atoms at the Ru(001)-p(2×2)-O surface have a positive effect on selective dehydrogenation of the methoxy species to CO+H 2 and a blocking effect on CO bond breaking of the methoxy species.

  3. The Asian methanol market

    International Nuclear Information System (INIS)

    Nagase, Hideki

    1995-01-01

    For the purpose of this presentation, Asia has been broadly defined as a total of 15 countries, namely Japan, Korea, Taiwan, China, Hong Kong, the Philippines, Thailand, Malaysia, Singapore, Indonesia, Myanmar, India, Vietnam, Australia and New Zealand. In 1994 and the first half of 1995, the methanol industry and its derivative industries experienced hard time, because of extraordinarily high methanol prices. In spite of this circumstance, methanol demand in Asian countries has been growing steadily and remarkably, following Asian high economic growth. Most of this growth in demand has been and will continue to be met by outside supply. However, even with increased import of methanol from outside of Asia, as a result of this growth, Asian trade volume will be much larger in the coming years. Asian countries must turn their collective attention to making logistics and transportation for methanol and its derivatives more efficient in the Asian region to make better use of existing supply resources. The author reviews current economic growth as his main topic, and explains the forecast of the growth of methanol demand and supply in Asian countries in the near future

  4. Integrated methanol synthesis

    International Nuclear Information System (INIS)

    Jaeger, W.

    1982-01-01

    This invention concerns a plant for methanol manufacture from gasified coal, particularly using nuclear power. In order to reduce the cost of the hydrogen circuits, the methanol synthesis is integrated in the coal gasification plant. The coal used is gasified with hydration by means of hydrogen and the crude gas emerging, after cooling and separating the carbon dioxide and hydrogen sulphide, is mixed with the synthetic gas leaving the methane cracking furnace. This mixture is taken to the methanol synthesis and more than 90% is converted into methanol in one pass. The gas mixture remaning after condensation and separation of methanol is decomposed into three fractions in low temperature gas decomposition with a high proportion of unconverted carbon monoxide. The flow of methane is taken to the cracking furnace with steam, the flow of hydrogen is taken to the hydrating coal gasifier, and the flow of carbon monoxide is taken to the methanol synthesis. The heat required for cracking the methane can either be provided by a nuclear reactor or by the coke left after hydrating gasification. (orig./RB) [de

  5. Development of new membrane materials for direct methanol fuel cells

    NARCIS (Netherlands)

    Yildirim, M.H.

    2009-01-01

    Development of new membrane materials for direct methanol fuel cells Direct methanol fuel cells (DMFCs) can convert the chemical energy of a fuel directly into electrical energy with high efficiency and low emission of pollutants. DMFCs can be used as the power sources to portable electronic devices

  6. ENGINEERING BULLETIN: SUPERCRITICAL WATER OXIDATION

    Science.gov (United States)

    This engineering bulletin presents a description and status of supercritical water oxidation technology, a summary of recent performance tests, and the current applicability of this emerging technology. This information is provided to assist remedial project managers, contractors...

  7. Effect of sorbed methanol, current, and temperature on multicomponent transport in nafion-based direct methanol fuel cells.

    Science.gov (United States)

    Rivera, Harry; Lawton, Jamie S; Budil, David E; Smotkin, Eugene S

    2008-07-24

    The CO2 in the cathode exhaust of a liquid feed direct methanol fuel cell (DMFC) has two sources: methanol diffuses through the membrane electrode assembly (MEA) to the cathode where it is catalytically oxidized to CO2; additionally, a portion of the CO2 produced at the anode diffuses through the MEA to the cathode. The potential-dependent CO2 exhaust from the cathode was monitored by online electrochemical mass spectrometry (ECMS) with air and with H2 at the cathode. The precise determination of the crossover rates of methanol and CO2, enabled by the subtractive normalization of the methanol/air to the methanol/H2 ECMS data, shows that methanol decreases the membrane viscosity and thus increases the diffusion coefficients of sorbed membrane components. The crossover of CO2 initially increases linearly with the Faradaic oxidation of methanol, reaches a temperature-dependent maximum, and then decreases. The membrane viscosity progressively increases as methanol is electrochemically depleted from the anode/electrolyte interface. The crossover maximum occurs when the current dependence of the diffusion coefficients and membrane CO2 solubility dominate over the Faradaic production of CO2. The plasticizing effect of methanol is corroborated by measurements of the rotational diffusion of TEMPONE (2,2,6,6-tetramethyl-4-piperidone N-oxide) spin probe by electron spin resonance spectroscopy. A linear inverse relationship between the methanol crossover rate and current density confirms the absence of methanol electro-osmotic drag at concentrations relevant to operating DMFCs. The purely diffusive transport of methanol is explained in terms of current proton solvation and methanol-water incomplete mixing theories.

  8. Direct Methanol Fuel Cell, DMFC

    Directory of Open Access Journals (Sweden)

    Amornpitoksuk, P.

    2003-09-01

    Full Text Available Direct Methanol Fuel Cell, DMFC is a kind of fuel cell using methanol as a fuel for electric producing. Methanol is low cost chemical substance and it is less harmful than that of hydrogen fuel. From these reasons it can be commercial product. The electrocatalytic reaction of methanol fuel uses Pt-Ru metals as the most efficient catalyst. In addition, the property of membrane and system designation are also effect to the fuel cell efficient. Because of low power of methanol fuel cell therefore, direct methanol fuel cell is proper to use for the energy source of small electrical devices and vehicles etc.

  9. Multi-walled carbon nanotubes (MWCNTs) functionalized with amino groups by reacting with supercritical ammonia fluids

    International Nuclear Information System (INIS)

    Shao Lu; Bai Yongping; Huang Xu; Gao Zhangfei; Meng Linghui; Huang Yudong; Ma Jun

    2009-01-01

    For the first time, supercritical ammonia fluid was utilized to simply functionalize multi-walled carbon nanotube (MWCNT) with amino groups. The successful amino functionalization of MWCNTs was proven and the physicochemical properties of MWCNTs before and after supercritical ammonia fluids modifications were characterized using X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM), atomic force microscope (AFM) and Raman spectroscopy. The results also indicated that the supercritical ammonia fluids had the visible effects on the nanostructure of carbon nanotubes. Our novel modification approach provides an easy way to modify MWCNTs with amino groups, which is very useful for realizing 'carbon nanotube economy' in the near future.

  10. Efficient separation of curcumin, demethoxycurcumin, and bisdemethoxycurcumin from turmeric using supercritical fluid chromatography: From analytical to preparative scale.

    Science.gov (United States)

    Song, Wei; Qiao, Xue; Liang, Wen-fei; Ji, Shuai; Yang, Lu; Wang, Yuan; Xu, Yong-wei; Yang, Ying; Guo, De-an; Ye, Min

    2015-10-01

    Curcumin is the major constituent of turmeric (Curcuma longa L.). It has attracted widespread attention for its anticancer and anti-inflammatory activities. The separation of curcumin and its two close analogs, demethoxycurcumin and bisdemethoxycurcumin, has been challenging by conventional techniques. In this study, an environmentally friendly method based on supercritical fluid chromatography was established for the rapid and facile separation of the three curcuminoids directly from the methanol extract of turmeric. The method was first developed and optimized by ultra performance convergence chromatography, and was then scaled up to preparative supercritical fluid chromatography. Eluted with supercritical fluid CO2 containing 8-15% methanol (containing 10 mM oxalic acid) at a flow rate of 80 mL/min, curcumin, demethoxycurcumin and bisdemethoxycurcumin could be well separated on a Viridis BEH OBD column (Waters, 250 mm × 19 mm, 5 μm) within 6.5 min. As a result, 20.8 mg of curcumin (97.9% purity), 7.0 mg of demethoxycurcumin (91.1%), and 4.6 mg of bisdemethoxycurcumin (94.8%) were obtained after a single step of supercritical fluid chromatography separation with a mean recovery of 76.6%. Showing obvious advantages in low solvent consumption, large sample loading, and easy solvent removal, supercritical fluid chromatography was proved to be a superior technique for the efficient separation of natural products. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Biodiesel production with continuous supercritical process: non-catalytic transesterification and esterification with or without carbon dioxide.

    Science.gov (United States)

    Tsai, Yu-Ting; Lin, Ho-mu; Lee, Ming-Jer

    2013-10-01

    The non-catalytic transesterification of refined sunflower oil with supercritical methanol, in the presence of carbon dioxide, was conducted in a tubular reactor at temperatures from 553.2 to 593.2K and pressures up to 25.0 MPa. The FAME yield can be achieved up to about 0.70 at 593.2 K and 10.0 MPa in 23 min with methanol:oil of 25:1 in molar ratio. The effect of adding CO2 on the FAME yield is insignificant. The kinetic behavior of the non-catalytic esterification and transesterification of oleic acid or waste cooking oil (WCO) with supercritical methanol was also investigated. By using the supercritical process, the presence of free fatty acid (FFA) in WCO gives positive contribution to FAME production. The FAME yield of 0.90 from WCO can be achieved in 13 min at 573.2K. The kinetic data of supercritical transesterification and esterifaication were correlated well with a power-law model. Copyright © 2012 Elsevier Ltd. All rights reserved.

  12. Methanol from biomass and hydrogen

    International Nuclear Information System (INIS)

    Anon.

    1989-01-01

    For Hawaii in the near term, the only liquid fuels indigenous sources will be those that can be made from biomass, and of these, methanol is the most promising. In addition, hydrogen produced by electrolysis can be used to markedly increase the yield of biomass methanol. This paper calculates cost of producing methanol by an integrated system including a geothermal electricity facility plus a plant producing methanol by gasifying biomass and adding hydrogen produced by electrolysis. Other studies cover methanol from biomass without added hydrogen and methanol from biomass by steam and carbon dioxide reforming. Methanol is made in a two-step process: the first is the gasification of biomass by partial oxidation with pure oxygen to produce carbon oxides and hydrogen, and the second is the reaction of gases to form methanol. Geothermal steam is used to generate the electricity used for the electrolysis to produce the added hydrogen

  13. A simple analysis of the stable field profile in the supercritical TEA

    DEFF Research Database (Denmark)

    Jeppesen, Palle; Jeppsson, B.

    1973-01-01

    An analytical investigation supported by numerical calculations has been performed of the stable field profile in a supercritical diffusion-stabilized n-GaAs transferred electron amplifier (TEA) with ohmic contacts. In the numerical analysis, the field profile is determined by solving the steady......}{2}} (n_{0}L)^{frac{1}{2}}. Those results contribute to the understanding of the highn_{0}L-product switch and the stability of the supercritical TEA....

  14. Technology with Supercritical Fluid. Part 2. Applications

    International Nuclear Information System (INIS)

    Marongiu, B.; De Giorgi, M. R.; Porcedda, S.; Cadoni, E.

    1998-01-01

    The present article is based on a bibliographical analysis of the main applications of the supercritical fluid in various fields, as: extraction from solid matrices, division of liquid charges, chromatography HPLC with supercritical eluent, chemical and biochemical reactions in supercritical solvents etc [it

  15. Methanol production by Mycobacterium smegmatis

    International Nuclear Information System (INIS)

    Weisman, L.S.; Ballou, C.E.

    1988-01-01

    Mycobacterium smegmatis cells produce [ 3 H]methanol when incubated with [methyl- 3 H]methionine. The methanol is derived from S-adenosylmethionine rather than methyltetrahydrofolate. M. smegmatis cells carboxymethylate several proteins, and some of the methanol probably results from their demethylation, but most of the methanol may come from an unidentified component with a high gel mobility. Although methanol in the medium reached 19 μM, it was not incorporated into the methylated mannose polysaccharide, a lipid carrier in this organism

  16. Hot new gamble on methanol

    Energy Technology Data Exchange (ETDEWEB)

    Hatton, J.

    1981-10-01

    Methanol from coal, wood, or natural gas is being considered as an extender or an alternative source of gasoline. Firms such as Nova and Celanese are gambling millions on the proposition that methanol is a crucial steppingstone to the fuels and chemicals of the future. With a new process developed by Mobil Oil, methanol from coal could be converted into gasoline. By the 1990s Imperial Oil Ltd. expects there will be at least one methanol plant using Alberta coal. These and other plans by the Alberta and British Columbia governments and by Canadian industry to produce methanol are reported.

  17. Methanol commercial aviation fuel

    International Nuclear Information System (INIS)

    Price, R.O.

    1992-01-01

    Southern California's heavy reliance on petroleum-fueled transportation has resulted in significant air pollution problems within the south Coast Air Basin (Basin) which stem directly from this near total dependence on fossil fuels. To deal with this pressing issue, recently enacted state legislation has proposed mandatory introduction of clean alternative fuels into ground transportation fleets operating within this area. The commercial air transportation sector, however, also exerts a significant impact on regional air quality which may exceed emission gains achieved in the ground transportation sector. This paper addresses the potential, through the implementation of methanol as a commercial aviation fuel, to improve regional air quality within the Basin and the need to flight test and demonstrate methanol as an environmentally preferable fuel in aircraft turbine engines

  18. Methanol and carbonylation

    Energy Technology Data Exchange (ETDEWEB)

    Gauthier-Lafaye, J.; Perron, R.

    1987-01-01

    The overall focus of the book is on homogeneous catalysed processes which were seen to offer the most promising routes to C/sub 2/ oxygenates. The first three chapters review the industrial synthesis and applications of carbon monoxide such as in the manufacture of gasoline (e.g. Fischer-Tropsch, Mobil processes), organic chemicals (e.g. ethanol, acetic acid, etc.), industrial importance of C/sub 2/ oxygenates, and use of methanol as a future feedstock are discussed. The next six chapters are each concerned with the production of a particular C/sub 2/ oxygenate and a detailed analysis of the methods and catalysts used. The hydrocarbonylation of methanol occupies a large chapter (136 references) with a comparative examination of the catalysts available, and their modification to increase selectivity to either acetylaldehyde or ethanol. Following chapters examine the synthesis of ethyl acetate, acetic acid, acetic anhydride, vinyl acetate, ethylene glycol and oxalic acid.

  19. Nitrofurantoin methanol monosolvate

    Directory of Open Access Journals (Sweden)

    Venu R. Vangala

    2011-03-01

    Full Text Available The antibiotic nitrofurantoin {systematic name: (E-1-[(5-nitro-2-furylmethylideneamino]imidazolidine-2,4-dione} crystallizes as a methanol monosolvate, C8H6N4O5·CH4O. The nitrofurantoin molecule adopts a nearly planar conformation (r.m.s. deviation = 0.0344 Å. Hydrogen bonds involve the co-operative N—H...O—H...O heterosynthons between the cyclic imide of nitrofurantoin and methanol O—H groups. There are also C—H...O hydrogen bonds involving the nitrofurantoin molecules which support the key hydrogen-bonding synthon. The overall crystal packing is further assisted by weak C—H...O interactions, giving a herringbone pattern.

  20. SnO2/carbon nanotube nanocomposites synthesized in supercritical fluids: highly efficient materials for use as a chemical sensor and as the anode of a lithium-ion battery

    International Nuclear Information System (INIS)

    An Guimin; Na Na; Zhang Xinrong; Miao Zhenjiang; Miao Shiding; Ding Kunlun; Liu Zhimin

    2007-01-01

    SnO 2 /multi-walled carbon nanotube (MWCNT) nanocomposites were prepared via oxidation of SnCl 2 in a supercritical CO 2 -methanol mixture containing MWCNTs. The as-prepared nanocomposites were characterized by means of x-ray diffraction, x-ray photoelectron spectroscopy, and transmission electron microscopy. It was indicated that SnO 2 nanoparticles with size of 3-5 nm were uniformly and tightly decorated on the MWCNTs. The chemiluminescence characteristic to H 2 S and electrochemical performance of the as-prepared SnO 2 /MWCNT composites were investigated. The SnO 2 /MWCNT composites exhibited extremely high efficiency for detecting H 2 S, and also displayed good electrochemical performance as the anode material in a lithium-ion battery

  1. Deciphering Periodic Methanol Masers

    Science.gov (United States)

    Stecklum, Bringfried; Caratti o Garatti, Alessio; Henning, Thomas; Hodapp, Klaus; Hopp, Ulrich; Kraus, Alex; Linz, Hendrik; Sanna, Alberto; Sobolev, Andrej; Wolf, Verena

    2018-05-01

    Impressive progress has been made in recent years on massive star formation, yet the involved high optical depths even at submm/mm wavelengths make it difficult to reveal its details. Recently, accretion bursts of massive YSOs have been identified to cause flares of Class II methanol masers (methanol masers for short) due to enhanced mid-IR pumping. This opens a new window to protostellar accretion variability, and implies that periodic methanol masers hint at cyclic accretion. Pinning down the cause of the periodicity requires joint IR and radio monitoring. We derived the first IR light curve of a periodic maser host from NEOWISE data. The source, G107.298+5.639, is an intermediate-mass YSO hosting methanol and water masers which flare every 34.5 days. Our recent joint K-band and radio observations yielded first but marginal evidence for a phase lag between the rise of IR and maser emission, respectively, and revealed that both NEOWISE and K-band light curves are strongly affected by the light echo from the ambient dust. Both the superior resolution of IRAC over NEOWISE and the longer wavelengths compared to our ground-based imaging are required to inhibit the distractive contamination by the light echo. Thus, we ask for IRAC monitoring of G107 to cover one flare cycle, in tandem with 100-m Effelsberg and 2-m Wendelstein radio and NIR observations to obtain the first high-quality synoptic measurements of this kind of sources. The IR-maser phase lag, the intrinsic shape of the IR light curves and their possible color variation during the cycle allow us to constrain models for the periodic maser excitation. Since methanol masers are signposts of intermediate-mass and massive YSOs, deciphering their variability offers a clue to the dynamics of the accretion-mediated growth of massive stars and their feedback onto the immediate natal environment. The Spitzer light curve of such a maser-hosting YSO would be a legacy science product of the mission.

  2. A supercritical carbon dioxide plasma process for preparing tungsten oxide nanowires

    International Nuclear Information System (INIS)

    Kawashima, Ayato; Nomura, Shinfuku; Toyota, Hiromichi; Takemori, Toshihiko; Mukasa, Shinobu; Maehara, Tsunehiro

    2007-01-01

    A supercritical carbon dioxide (CO 2 ) plasma process for fabricating one-dimensional tungsten oxide nanowires coated with amorphous carbon is presented. High-frequency plasma was generated in supercritical carbon dioxide at 20 MPa by using tungsten electrodes mounted in a supercritical cell, and subsequently an organic solvent was introduced with supercritical carbon dioxide into the plasma. Electron microscopy and Raman spectroscopy investigations of the deposited materials showed the production of tungsten oxide nanowires with or without an outer layer. The nanowires with an outer layer exhibited a coaxial structure with an outer concentric layer of amorphous carbon and an inner layer of tungsten oxide with a thickness and diameter of 20-30 and 10-20 nm, respectively

  3. Supercritical Carbon Dioxide–Based Sterilization of Decellularized Heart Valves

    Directory of Open Access Journals (Sweden)

    Ryan S. Hennessy, MD

    2017-02-01

    Full Text Available Summary: Sterilization of grafts is essential. Supercritical carbon dioxide, electrolyzed water, gamma radiation, ethanol-peracetic acid, and hydrogen peroxide techniques were compared for impact on sterility and mechanical integrity of porcine decellularized aortic valves. Ethanol-peracetic acid– and supercritical carbon dioxide–treated valves were found to be sterile using histology, microbe culture, and electron microscopy assays. The cusp tensile properties of supercritical carbon dioxide–treated valves were higher compared with valves treated with other techniques. Superior sterility and integrity was found in the decellularized valves treated with supercritical carbon dioxide sterilization. This sterilization technique may hold promise for other decellularized soft tissues. Key Words: decellularized, decontamination, heart valve, tensile properties, tissue engineering

  4. Biological conversion of biogas to methanol using methanotrophs isolated from solid-state anaerobic digestate.

    Science.gov (United States)

    Sheets, Johnathon P; Ge, Xumeng; Li, Yueh-Fen; Yu, Zhongtang; Li, Yebo

    2016-02-01

    The aim of this work was to isolate methanotrophs (methane oxidizing bacteria) that can directly convert biogas produced at a commercial anaerobic digestion (AD) facility to methanol. A methanotrophic bacterium was isolated from solid-state anaerobic digestate. The isolate had characteristics comparable to obligate methanotrophs from the genus Methylocaldum. This newly isolated methanotroph grew on biogas or purified CH4 and successfully converted biogas from AD to methanol. Methanol production was achieved using several methanol dehydrogenase (MDH) inhibitors and formate as an electron donor. The isolate also produced methanol using phosphate with no electron donor or using formate with no MDH inhibitor. The maximum methanol concentration (0.43±0.00gL(-1)) and 48-h CH4 to methanol conversion (25.5±1.1%) were achieved using biogas as substrate and a growth medium containing 50mM phosphate and 80mM formate. Copyright © 2015 Elsevier Ltd. All rights reserved.

  5. The (p, ρ, T) of (methanol + benzene) and (methanol + ethylbenzene)

    International Nuclear Information System (INIS)

    Naziev, Yashar M.; Shahverdiyev, Astan N.; Hasanov, Vaqif H.

    2005-01-01

    The (p, ρ, T) of methanol, ethylbenzene and (methanol + benzene) and (methanol + ethylbenzene) at temperatures between (290 and 500) K and pressures in the range (0.1 to 60) MPa have been measured with a magnetic suspension densimeter with an uncertainty of ±0.1%. Our measurements with methanol deviate from the literature values by less than 0.2%. The (p, ρ, T) measurements were fitted with experimental uncertainties by an empirical equation. The temperature and mole fraction dependence of the coefficients of the equation of state are presented

  6. Formaldehyde, methanol and hydrocarbon emissions from methanol-fueled cars

    International Nuclear Information System (INIS)

    Williams, R.L.; Lipari, F.; Potter, R.A.

    1990-01-01

    Exhaust and evaporative emissions tests were conducted on several methanol- and gasoline-fueled vehicles. Separate samples for chromatographic analysis of formaldehyde, methanol, and individual hydrocarbons were collected in each of the three phases of the driving cycle and in each of the two portions of the evaporative emissions test. One vehicle, equipped with an experimental variable-fuel engine, was tested using methanol/gasoline fuel mixtures of 100, 85, 50, 15, and 0 percent methanol. Combustion-generated hydrocarbons were lowest using methanol fuel, and increased several-fold as the gasoline fraction was increased. Gasoline components in the exhaust increased from zero as the gasoline fraction of the fuel was increased. On the other hand, formaldehyde emissions were several times higher using methanol fuel than they were using gasoline. A dedicated methanol car and the variable-fuel car gave similar emissions patterns when they both were tested using methanol fuel. The organic-carbon composition of the exhaust was 85-90 percent methanol, 5-7 percent formaldehyde, and 3-9 percent hydrocarbons. Several cars that were tested using gasoline emitted similar distributions of hydrocarbons, even through the vehicles represented a broad range of current and developmental engine families and emissions control systems

  7. Structural Study of Reduced Graphene Oxide/ Polypyrrole Composite as Methanol Sensor in Direct Methanol Fuel Cell

    International Nuclear Information System (INIS)

    Mumtazah Atiqah Hassan; Siti Kartom Kamarudin; Siti Kartom Kamarudin

    2016-01-01

    Density functional theory (DFT) computations were performed on the optimized geometric and electronic properties of reduced graphene oxide/polypyrole (rGO/ PPy) composite in comparison with pure graphene and graphene oxide structures. Incorporation of both reduced GO (rGO) and PPy will form a good composite which have advantages from both materials such as good mechanical strength and excellent electrical conductivity. These composite would be very suitable in fabrication of methanol sensor in direct methanol fuel cell (DMFC). The HOMO-LUMO energy (eV) was also calculated. These computations provide a theoretical explanation for the good performance of rGO/ PPy composite as electrode materials in methanol sensor. (author)

  8. Methanol utilizing Desulfotomaculum species utilizes hydrogen in a methanol-fed sulfate-reducing bioreactor.

    Science.gov (United States)

    Balk, Melike; Weijma, Jan; Goorissen, Heleen P; Ronteltap, Mariska; Hansen, Theo A; Stams, Alfons J M

    2007-01-01

    A sulfate-reducing bacterium, strain WW1, was isolated from a thermophilic bioreactor operated at 65 degrees C with methanol as sole energy source in the presence of sulfate. Growth of strain WW1 on methanol or acetate was inhibited at a sulfide concentration of 200 mg l(-1), while on H2/CO2, no apparent inhibition occurred up to a concentration of 500 mg l(-1). When strain WW1 was co-cultured under the same conditions with the methanol-utilizing, non-sulfate-reducing bacteria, Thermotoga lettingae and Moorella mulderi, both originating from the same bioreactor, growth and sulfide formation were observed up to 430 mg l(-1). These results indicated that in the co-cultures, a major part of the electron flow was directed from methanol via H2/CO2 to the reduction of sulfate to sulfide. Besides methanol, acetate, and hydrogen, strain WW1 was also able to use formate, malate, fumarate, propionate, succinate, butyrate, ethanol, propanol, butanol, isobutanol, with concomitant reduction of sulfate to sulfide. In the absence of sulfate, strain WW1 grew only on pyruvate and lactate. On the basis of 16S rRNA analysis, strain WW1 was most closely related to Desulfotomaculum thermocisternum and Desulfotomaculum australicum. However, physiological properties of strain WW1 differed in some aspects from those of the two related bacteria.

  9. Optimization and kinetic studies of sea mango (Cerbera odollam) oil for biodiesel production via supercritical reaction

    International Nuclear Information System (INIS)

    Ang, Gaik Tin; Ooi, San Nee; Tan, Kok Tat; Lee, Keat Teong; Mohamed, Abdul Rahman

    2015-01-01

    Highlights: • Sea mango oil as feedstock for biodiesel via non-catalytic supercritical reaction. • Extracted sea mango oil with high FFA could produce high yield of FAME. • Employment of Response Surface Methodology for optimization of FAME. • Kinetic study for reversible transesterification and esterification reactions. - Abstract: Sea mango (Cerbera odollam) oil, which is rich in free fatty acids, was utilized to produce fatty acid methyl esters (FAME) via supercritical transesterification reaction. Sea mango oil was extracted from seeds and was subsequently reacted with methanol in a batch-type supercritical reactor. Response surface methodology (RSM) analysis was used to optimize important parameters, including reaction temperature, reaction time and the molar ratio of methanol to oil. The optimum conditions were found as 380 °C, 40 min and 45:1 mol/mol, respectively, to achieve 78% biodiesel content. The first kinetic modelling of FAME production from sea mango oil incorporating reversible transesterification and reversible esterification was verified simultaneously. The kinetic parameters, including reaction rate constants, k, the pre-exponential constant, A, and the activation energy, Ea, for transesterification and esterification were determined using an ordinary differential equation (ODE45) solver. The highest activation energy of 40 kJ/mol and the lowest reaction rate constant of 2.50 × 10 −5 dm 3 /mol s verified that the first stepwise reaction of TG to produce DG was the rate-limiting step

  10. Phase equilibrium of binary system carbon dioxide - methanol at high pressure using artificial neural network

    International Nuclear Information System (INIS)

    Nasri, F.; Hatami, T.

    2012-01-01

    Interest in supercritical fluids extraction (SFE ) is increasing throughout many scientific and industrial fields. The common solvent for use in SFE is carbon dioxide. However, pure carbon dioxide frequently fails to efficiently extract the essential oil from a sample matrix, and modifier fluids such as methanol should be used to enhance extraction yield. A more efficient use of SFE requires quantitative prediction of phase equilibrium of this binary system, carbon dioxide - methanol. The purpose of the current research is modeling carbon dioxide - methanol system using artificial neural network (ANN). Results of ANN modeling has been compared with experimental data as well as thermodynamic equations of state. The comparison shows that the ANN modeling has a higher accuracy than thermodynamic models. (author)

  11. Synthesis pf dimethyl carbonate in supercritical carbon dioxide

    Energy Technology Data Exchange (ETDEWEB)

    Ballivet-Tkatchenko, D.; Plasseraud, L. [Universite de Bourgogne-UFR Sciences et Techniques, Dijon (France). Lab. de Synthese et Electrosynthese Organometalliques]. E-mail: ballivet@u-bourgogne.fr; Ligabue, R.A. [Pontificia Univ. Catolica do Rio Grande do Sul, Porto Alegre, RS (Brazil). Dept. de Quimica Pura

    2006-01-15

    The reactivity of carbon dioxide with methanol to form dimethyl carbonate was studied in the presence of the n-butylmethoxytin compounds n-Bu{sub 3}SnOCH{sub 3}, n-Bu{sub 2}Sn(OCH{sub 3}){sub 2}, and [n-Bu{sub 2}(CH{sub 3}O)Sn]{sub 2}O. The reaction occurred under solventless conditions at 423 K and was produced by an increase in CO{sub 2} pressure. This beneficial effect is primarily attributed to phase behavior. The mass transfer under liquid-vapor biphasic conditions was not limiting when the system reached the supercritical state for a CO{sub 2} pressure higher than 16 MPa. Under these conditions, CO{sub 2} acted as a reactant and a solvent. (author)

  12. Drying of supercritical carbon dioxide with membrane processes

    NARCIS (Netherlands)

    Lohaus, Theresa; Scholz, Marco; Koziara, Beata; Benes, Nieck Edwin; Wessling, Matthias

    2015-01-01

    In supercritical extraction processes regenerating the supercritical fluid represents the main cost constraint. Membrane technology has potential for cost efficient regeneration of water-loaded supercritical carbon dioxide. In this study we have designed membrane-based processes to dehydrate

  13. Comparison of Biodiesel Obtained from Virgin Cooking Oil and Waste Cooking Oil Using Supercritical and Catalytic Transesterification

    Directory of Open Access Journals (Sweden)

    Jeeban Poudel

    2017-04-01

    Full Text Available Comparative analysis of transesterification of virgin cooking oil (VCO and waste cooking oil (WCO in catalyzed and supercritical transesterification process using methanol and ethanol as solvents has been conducted in this study. The luminous point of this research was the direct comparison of catalytic and supercritical process using the ester composition obtained from virgin cooking oil and waste cooking oil transesterification. Oil to alcohol molar ratio of 1:6 and reaction condition of 65 °C and 1 bar pressure were considered for the catalytic process, while 260 °C and high pressure (65 and 75 bar for methanol and ethanol, respectively were accounted for the supercritical process. Distinct layer separation was observed for both processes. Ester, fatty acid and glycerol composition was studied for both the upper and lower layers separately, from which 100% ester composition in the upper layer and a mixture of ester and other composition in the lower layer was obtained for the catalytic process owing to succeeding filtration and washing. However, mixture of ester (>75% and other composition was obtained in both layers for the supercritical process where purification process was not implemented. The similarity in the result obtained demonstrates the superiority of waste cooking oil compared to virgin cooking oil, taking cost into consideration.

  14. Supercritical Fluid Extraction of Lovastatin from the Wheat Bran Obtained after Solid-State Fermentation

    Directory of Open Access Journals (Sweden)

    Ruchir C. Pansuriya

    2009-01-01

    Full Text Available The objective of the present work is to extract lovastatin with minimum impurity by using supercritical carbon dioxide (SC-CO2. A strain of Aspergillus terreus UV 1617 was used to produce lovastatin by solid-state fermentation (SSF on wheat bran as a solid substrate. Extraction of lovastatin and its hydroxy acid form was initially carried out using organic solvents. Among the different screened solvents, acetonitrile was found to be the most efficient. SC-CO2 was used for extraction of lovastatin from the dry fermented matter. The effect of supercritical extraction parameters such as the amount of an in situ pretreatment solvent, temperature, pressure, flow rate and contact time were investigated. The maximum recovery of lovastatin was obtained with 5 mL of methanol as an in situ pretreatment solvent for 1.5 g of solid matrix, flow rate of the supercritical solvent 2 L/min, temperature 50 °C, and contact time 155 min at a pressure 300 bar. The lovastatin extract obtained after optimizing the conditions of supercritical fluid extraction was found to have 5-fold more HPLC purity than the organic solvent extract.

  15. The shape of the electronic circular dichroism spectrum of (2,6-dimethylphenyl)(phenyl)methanol: interplay between conformational equilibria and vibronic effects.

    Science.gov (United States)

    Padula, Daniele; Cerezo, Javier; Pescitelli, Gennaro; Santoro, Fabrizio

    2017-12-13

    Comparison between chiroptical spectra and theoretical predictions is the method of choice for the assignment of the absolute configuration of chiral compounds in solution. Here we report the case of an apparently simple biarylcarbinol, whose electronic circular dichroism (ECD) in the 1 L b region exhibits a peculiar alternation of negative and positive bands. Adopting Density Functional Theory, and describing solvent effects with implicit methods, we found three stable conformers in ethanol, each of them with two close lying states corresponding to similar local 1 L b excitations on the two phenyls. We computed the corresponding vibronic ECD spectra in harmonic approximation, including Duschinsky mixings as well as both Franck Condon (FC) and Herzberg Teller (HT) effects. Exploiting a recently developed mixed quantum/classical method, we further investigated the contribution of the vibronic spectra of out-of-equilibrium structures along the interconversion path connecting the different conformers. In this way, we achieved a reasonable agreement with experiment and attributed the alternating signs of the bands to the existence of different conformers. The remaining discrepancies with experiment indicate that specific solute-solvent interactions modulate the relative conformers' stabilities, calling for new methods able to combine Molecular Dynamics explorations and vibronic calculations. Moreover, the poor performance of HT approaches and the existence of two closely-lying states suggest the necessity of an improved fully-nonadiabatic vibronic approach. These findings demonstrate that even for such a simple system as the biarylcarbinol investigated here, a full reproduction of the fine details of the ECD spectrum requires the development of new improved methods.

  16. PULSE RADIOLYSIS IN SUPERCRITICAL RARE GAS FLUIDS

    International Nuclear Information System (INIS)

    HOLROYD, R.

    2007-01-01

    Recently, supercritical fluids have become quite popular in chemical and semiconductor industries for applications in chemical synthesis, extraction, separation processes, and surface cleaning. These applications are based on: the high dissolving power due to density build-up around solute molecules, and the ability to tune the conditions of a supercritical fluid, such as density and temperature, that are most suitable for a particular reaction. The rare gases also possess these properties and have the added advantage of being supercritical at room temperature. Information about the density buildup around both charged and neutral species can be obtained from fundamental studies of volume changes in the reactions of charged species in supercritical fluids. Volume changes are much larger in supercritical fluids than in ordinary solvents because of their higher compressibility. Hopefully basic studies, such as discussed here, of the behavior of charged species in supercritical gases will provide information useful for the utilization of these solvents in industrial applications

  17. Development of methanol evaporation plate to reduce methanol crossover in a direct methanol fuel cell

    Science.gov (United States)

    Zhang, Ruiming

    This research focuses on methanol crossover reduction in direct methanol fuel cells (DMFC) through separating the methanol vapor from its liquid phase and feeding the vapor passively at low temperature range. Membrane electrode assemblies (MEAs) were fabricated by using commercial available membrane with different thickness at different anode catalyst loading levels, and tested under the operating conditions below 100°C in cell temperature and cathode exit open to ambient pressure. Liquid methanol transport from the anode through the membrane into cathode ("methanol crossover") is identified as one of the major efficiency losses in a DMFC. It is known that the methanol crossover rate in the vapor phase is much lower than in liquid phase. Vapor feed can be achieved by heating the liquid methanol to elevated temperatures (>100°C), but other issues limit the performance of the cell when operating above 100°C. High temperature membranes and much more active cathode catalyst structures are required, and a complex temperature control system must be employed. However, methanol vapor feed can also occur at a lower temperature range (evaporation through a porous body. The methanol crossover with this vapor feed mode is lower compared with the direct liquid methanol feed. A new method of using a methanol evaporation plate (MEP) to separate the vapor from its liquid phase to reduce the liquid methanol crossover at low temperature range is developed. A MEP plays the roles of liquid/vapor methanol phase separation and evaporation in a DMFC. The goal of this study is to develop a MEP with the proper properties to achieve high methanol phase separation efficiency and fast methanol evaporation rate over a wide range of temperature, i.e., from room temperature up to near boiling temperature (100°C). MEP materials were selected and characterized. MEPs made from three different types were tested extensively with different MEA and porous back layer configurations. The benefits of

  18. Influence of reaction conditions and type of alcohol on biodiesel yields and process economics of supercritical transesterification

    International Nuclear Information System (INIS)

    Micic, Radoslav D.; Tomić, Milan D.; Kiss, Ferenc E.; Nikolić-Djorić, Emilija B.; Simikić, Mirko Ð.

    2014-01-01

    Highlights: • Transesterification in supercritical methanol, ethanol and 1-propanol investigated. • Effect of alcohol, reaction temperature, pressure and time on yields analyzed. • Temperature has the highest impact on yield, followed by time and pressure. • Direct material and energy costs for each of the production alternatives estimated. • Lowest costs are achieved at highest yields even at very low oil prices. - Abstract: Experiments with transesterification of rapeseed oil in supercritical alcohols (methanol, ethanol and 1-propanol) were carried out in a batch reactor at various reaction temperatures (250–350 °C), working pressure (8–12 MPa), reaction time, and constant 42:1 alcohol to oil molar ratio. Influence of different alcohols and reaction conditions on biodiesel yield was investigated using linear multiple regression models. Temperature had the highest impact on yields, followed by reaction time and pressure. With increased molecular weight of alcohols, relative importance of temperature for explanation of yields decreased and relative importance of time and pressure increased. Economic assessment has revealed that transesterification in supercritical methanol has the lowest direct material and energy costs. Yield has crucial impact on process economics. Direct costs decrease with increase in biodiesel yields. Even at very low prices of oil feedstock the lowest cost is achieved at the highest yield

  19. A study on amphiphilic fluorinated block copolymer in graphite exfoliation using supercritical CO2 for stable graphene dispersion.

    Science.gov (United States)

    Kim, Young Hyun; Lee, Hyang Moo; Choi, Sung Wook; Cheong, In Woo

    2018-01-15

    In this study, poly(2,2,2-trifluoroethyl methacrylate)-block-poly(4-vinylpyridine) (PTFEMA-b-PVP) was synthesized by stepwise reversible addition-fragmentation chain transfer (RAFT) polymerization for the preparation of graphene by the exfoliation of graphite nanoplatelets (GPs) in supercritical CO 2 (SCCO 2 ). Two different block copolymers (low and high molecular weights) were prepared with the same block ratio and used at different concentrations in the SCCO 2 process. The amount of PTFEMA-b-PVP adsorbed on the GPs and the electrical conductivity of the SCCO 2 -treated GP samples were evaluated using thermogravimetric analysis (TGA) and four-point probe method, respectively. All GP samples treated with SCCO 2 were then dispersed in methanol and the dispersion stability was investigated using online turbidity measurements. The concentration and morphology of few-layer graphene stabilized with PTFEMA-b-PVP in the supernatant solution were investigated by gravimetry, scanning electron microscopy, and Raman spectroscopy. Destabilization study of the graphene dispersions revealed that the longer block copolymer exhibited better affinity for graphene, resulting in a higher yield of stable graphene with minimal defects. Copyright © 2017 Elsevier Inc. All rights reserved.

  20. Methanol as an energy carrier

    Energy Technology Data Exchange (ETDEWEB)

    Biedermann, P.; Grube, T.; Hoehlein, B. (eds.)

    2006-07-01

    For the future, a strongly growing energy demand is expected in the transport sector worldwide. Economically efficient oil production will run through a maximum in the next decade. Higher fuel prices and an environmentally desirable reduction of emissions will increase the pressure for reducing fuel consumption and emissions in road traffic. These criteria show the urgent necessity of structural changes in the fuel market. Due to its advantages concerning industrial-scale production, storage and global availability, methanol has the short- to medium-term potential for gaining increased significance as a substitution product in the energy market. Methanol can be produced both from fossil energy sources and from biomass or waste materials through the process steps of synthesis gas generation with subsequent methanol synthesis. Methanol has the potential to be used in an environmentally friendly manner in gasoline/methanol mixtures for flexible fuel vehicles with internal combustion engines and in diesel engines with pure methanol. Furthermore, it can be used in fuel cell vehicles with on-board hydrogen production in direct methanol fuel cell drives, and in stationary systems for electricity and heat generation as well as for hydrogen production. Finally, in portable applications it serves as an energy carrier for electric power generation. In this book, the processes for the production and use of methanol are presented and evaluated, markets and future options are discussed and issues of safety and environmental impacts are addressed by a team of well-known authors. (orig.)

  1. Methanol synthesis beyond chemical equilibrium

    NARCIS (Netherlands)

    van Bennekom, J. G.; Venderbosch, R. H.; Winkelman, J. G. M.; Wilbers, E.; Assink, D.; Lemmens, K. P. J.; Heeres, H. J.

    2013-01-01

    In commercial methanol production from syngas, the conversion is thermodynamically limited to 0.3-0.7 leading to large recycles of non-converted syngas. This problem can be overcome to a significant extent by in situ condensation of methanol during its synthesis which is possible nowadays due to the

  2. Injection of Fluids into Supercritical Environments

    National Research Council Canada - National Science Library

    Oschwald, M

    2004-01-01

    This paper summarizes and compares the results of systematic research programs at two independent laboratories regarding the injection of cryogenic liquids at subcritical and supercritical pressures...

  3. Mixing Dynamics of Supercritical Droplets and Jets

    National Research Council Canada - National Science Library

    Talley, Douglas G; Cohn, R. K; Coy, E. B; Chehroudi, B; Davis, D. W

    2005-01-01

    .... At supercritical pressures, however, a distinct difference between "gaseous" and "liquid" phases no longer exists, surface tension and the enthalpy of vaporization vanish, and "gas" phase density...

  4. Methylnaltrexone bromide methanol monosolvate

    Directory of Open Access Journals (Sweden)

    Xinbo Zhou

    2012-03-01

    Full Text Available In the title compound [systematic name: (4R,4aS,7aR,12bS-3-cyclopropylmethyl-4a,9-hydroxy-7-oxo-2,3,4,4a,5,6,7,7a-octahydro-1H-4,12-methanobenzofuro[3,2-e]isoquinolin-3-ium bromide methanol monosolvate], C21H26NO4+·Br−·CH3OH, two of the three six-membered rings adopt chair conformations while the third, which contains a C=C double bond, adopts an approximate half-boat conformation. The 2,3-dihydrofuran ring adopts an envelope conformation. In the crystal, the components are linked by O—H...O and O—H...Br hydrogen bonds. The absolute stereochemistry was inferred from one of the starting materials.

  5. Stable Amplification and High Current Drop Bistable Switching in Supercritical GaAs Tills

    DEFF Research Database (Denmark)

    Izadpanah, S.H; Jeppsson, B; Jeppesen, Palle

    1974-01-01

    Bistable switching with current drops of 40% and switching times of 100 ps are obtained in pulsed operation of 10¿m supercritically doped n+ nn+ GaAs Transferred Electron Devices (TEDs). When CW-operated the same devices exhibit a 5-17 GHz bandwidth for the stable negative resistance.......Bistable switching with current drops of 40% and switching times of 100 ps are obtained in pulsed operation of 10¿m supercritically doped n+ nn+ GaAs Transferred Electron Devices (TEDs). When CW-operated the same devices exhibit a 5-17 GHz bandwidth for the stable negative resistance....

  6. Lipidomics by Supercritical Fluid Chromatography

    Directory of Open Access Journals (Sweden)

    Laurent Laboureur

    2015-06-01

    Full Text Available This review enlightens the role of supercritical fluid chromatography (SFC in the field of lipid analysis. SFC has been popular in the late 1980s and 1990s before almost disappearing due to the commercial success of liquid chromatography (LC. It is only 20 years later that a regain of interest appeared when new commercial instruments were introduced. As SFC is fully compatible with the injection of extracts in pure organic solvent, this technique is perfectly suitable for lipid analysis and can be coupled with either highly universal (UV or evaporative light scattering or highly specific (mass spectrometry detection methods. A short history of the use of supercritical fluids as mobile phase for the separation oflipids will be introduced first. Then, the advantages and drawbacks of SFC are discussed for each class of lipids (fatty acyls, glycerolipids, glycerophospholipids, sphingolipids, sterols, prenols, polyketides defined by the LIPID MAPS consortium.

  7. Lipidomics by Supercritical Fluid Chromatography

    Science.gov (United States)

    Laboureur, Laurent; Ollero, Mario; Touboul, David

    2015-01-01

    This review enlightens the role of supercritical fluid chromatography (SFC) in the field of lipid analysis. SFC has been popular in the late 1980s and 1990s before almost disappearing due to the commercial success of liquid chromatography (LC). It is only 20 years later that a regain of interest appeared when new commercial instruments were introduced. As SFC is fully compatible with the injection of extracts in pure organic solvent, this technique is perfectly suitable for lipid analysis and can be coupled with either highly universal (UV or evaporative light scattering) or highly specific (mass spectrometry) detection methods. A short history of the use of supercritical fluids as mobile phase for the separation oflipids will be introduced first. Then, the advantages and drawbacks of SFC are discussed for each class of lipids (fatty acyls, glycerolipids, glycerophospholipids, sphingolipids, sterols, prenols, polyketides) defined by the LIPID MAPS consortium. PMID:26090714

  8. Supercritical fluid regeneration of adsorbents

    Science.gov (United States)

    Defilippi, R. P.; Robey, R. J.

    1983-05-01

    The results of a program to perform studies supercritical (fluid) carbon dioxide (SCF CO2) regeneration of adsorbents, using samples of industrial wastewaters from manufacturing pesticides and synthetic solution, and to estimate the economics of the specific wastewater treatment regenerations, based on test data are given. Processing costs for regenerating granular activated carbon GAC) for treating industrial wastewaters depend on stream properties and regeneration throughput.

  9. Recuperative supercritical carbon dioxide cycle

    Science.gov (United States)

    Sonwane, Chandrashekhar; Sprouse, Kenneth M; Subbaraman, Ganesan; O'Connor, George M; Johnson, Gregory A

    2014-11-18

    A power plant includes a closed loop, supercritical carbon dioxide system (CLS-CO.sub.2 system). The CLS-CO.sub.2 system includes a turbine-generator and a high temperature recuperator (HTR) that is arranged to receive expanded carbon dioxide from the turbine-generator. The HTR includes a plurality of heat exchangers that define respective heat exchange areas. At least two of the heat exchangers have different heat exchange areas.

  10. Supercritical Water Mixture (SCWM) Experiment

    Science.gov (United States)

    Hicks, Michael C.; Hegde, Uday G.

    2012-01-01

    The subject presentation, entitled, Supercritical Water Mixture (SCWM) Experiment, was presented at the International Space Station (ISS) Increment 33/34 Science Symposium. This presentation provides an overview of an international collaboration between NASA and CNES to study the behavior of a dilute aqueous solution of Na2SO4 (5% w) at near-critical conditions. The Supercritical Water Mixture (SCWM) investigation, serves as important precursor work for subsequent Supercritical Water Oxidation (SCWO) experiments. The SCWM investigation will be performed in DECLICs High Temperature Insert (HTI) for the purpose of studying critical fluid phenomena at high temperatures and pressures. The HTI includes a completely sealed and integrated test cell (i.e., Sample Cell Unit SCU) that will contain approximately 0.3 ml of the aqueous test solution. During the sequence of tests, scheduled to be performed in FY13, temperatures and pressures will be elevated to critical conditions (i.e., Tc = 374C and Pc = 22 MPa) in order to observe salt precipitation, precipitate agglomeration and precipitate transport in the presence of a temperature gradient without the influences of gravitational forces. This presentation provides an overview of the motivation for this work, a description of the DECLIC HTI hardware, the proposed test sequences, and a brief discussion of the scientific research objectives.

  11. Process intensification for biodiesel production from Jatropha curcas L. seeds: Supercritical reactive extraction process parameters study

    International Nuclear Information System (INIS)

    Lim, Steven; Lee, Keat Teong

    2013-01-01

    Highlights: ► Investigation of supercritical reactive extraction process for biodiesel production. ► Focus is given on optimizing methyl esters yield for Jatropha curcas L. seeds. ► Influence of process parameters to the reaction are discussed thoroughly. ► Comparison between the novel reaction with conventional process are studied. ► High methyl esters yield can be obtained without pre-extraction and catalyst. -- Abstract: In a bid to increase the cost competitiveness of biodiesel production against mineral diesel, process intensification has been studied for numerous biodiesel processing technologies. Subsequently, reactive extraction or in situ transesterification is actively being explored in which the solid oil-bearing seeds are used as the reactant directly with short-chain alcohol. This eliminates separate oil extraction process and combines both extraction and transesterification in a single unit. Supercritical reactive extraction takes one step further by substituting the role of catalyst with supercritical conditions to achieve higher yield and shorter processing time. In this work, supercritical reactive extraction with methanol was carried out in a high-pressure batch reactor to produce fatty acid methyl esters (FAMEs) from Jatropha curcas L. seeds. Material and process parameters including space loading, solvent to seed ratio, co-solvent (n-hexane) to seed ratio, reaction temperature, reaction time and mixing intensity were varied one at a time and optimized based on two responses i.e. extraction efficiency, M extract and FAME yield, F y . The optimum responses for supercritical reactive extraction obtained were 104.17% w/w and 99.67% w/w (relative to 100% lipid extraction with n-hexane) for M extract and F y respectively under the following conditions: 54.0 ml/g space loading, 5.0 ml/g methanol to seeds ratio, 300 °C, 9.5 MPa (Mega Pascal), 30 min reaction time and without n-hexane as co-solvent or any agitation source. This proved that

  12. Photolysis of oxyfluorfen in aqueous methanol.

    Science.gov (United States)

    Chakraborty, Subhasish K; Chakraborty, Savitri; Bhattacharyya, Anjan; Chowdhury, Ashim

    2013-01-01

    Photolysis of oxyfluorfen, an herbicide of the nitrodiphenyl ether class, was studied in aqueous methanol under UV and sunlight. UV irradiation was carried out in a borosilicate glass photoreactor (containing 250 ppm oxyfluorfen in 50% aqueous methanol) equipped with a quartz filter and 125 watt mercury lamp (maximum output 254 nm) at 25 ± 1°C. Sunlight irradiation was conducted at 28 ± 1°C in borosilicate Erlenmeyer flasks containing 250 ppm oxyfluorfen in 50% aqueous methanol. The samples from both the irradiated conditions were withdrawn at a definite time interval and extracted to measure oxyfluorfen content by gas chromatography-flame ionization detector for rate study. The half-life values were 20 hours and 2.7 days under UV and sunlight exposure, respectively. Photolysis of oxyfluorfen yielded 13 photoproducts of which three were characterized by infrared spectrophotometer and (1)H NMR and (13)C NMR spectroscopy. The rest of the photoproducts were identified by gas chromatography-mass spectrometry (GC-MS) and thin layer chromatography (TLC). An ionization potential 70 eV was used for electron impact-mass spectrometry (EI-MS) and methane was used as reagent gas for chemical ionization-mass spectrometry (CI-MS). Two of the photoproducts were also synthesized for comparison. The main phototransformation pathways of oxyfluorfen involved nitro reduction, dechlorination, and hydrolysis as well as nucleophiles displacement reaction.

  13. [Study on condition for extraction of arctiin from fruits of Arctium lappa using supercritical fluid extraction].

    Science.gov (United States)

    Dong, Wen-hong; Liu, Ben

    2006-08-01

    To study the feasibility of supercritical fluid extraction (SFE) for arctiin from the fruits of Arctium lappa. The extracts were analyzed by HPLC, optimum extraction conditions were studied by orthogonal tests. The optimal extraction conditions were: pressure 40 MPa, temperature 70 degrees C, using methanol as modifier carrier at the rate of 0.55 mL x min(-1), static extraction time 5 min, dynamic extraction 30 min, flow rate of CO2 2 L x min(-1). SFE has the superiority of adjustable polarity, and has the ability of extracting arctiin.

  14. Nanotechnology and supercritical fluids | Hamidreza | Journal of ...

    African Journals Online (AJOL)

    Supercritical fluid (SCF) technology has become an important tool of materials processing in the last two decades. Supercritical CO2 and H2O are extensively being used in the preparation of a great variety of nanomaterials. The interest in the preparation and application of nanometer size materials is increasing since they ...

  15. Transport properties of supercritical carbon dioxide

    NARCIS (Netherlands)

    Lavanchy, F.; Fourcade, E.; de Koeijer, E.A.; Wijers, J.G.; Meyer, T.; Keurentjes, J.T.F.; Kemmere, M.F.; Meyer, T.

    2005-01-01

    Recently, supercritical fluids have emerged as more sustainable alternatives for the organic solvents often used in polymer processes. This is the first book emphasizing the potential of supercritical carbon dioxide for polymer processes from an engineering point of view. It develops a

  16. Rapid Determination of Two Triterpenoid Acids in Chaenomelis Fructus Using Supercritical Fluid Extraction On-line Coupled with Supercritical Fluid Chromatography.

    Science.gov (United States)

    Zhang, Xiaotian; Ji, Feng; Li, Yueqi; He, Tian; Han, Ya; Wang, Daidong; Lin, Zongtao; Chen, Shizhong

    2018-01-01

    In this study, an on-line supercritical fluid extraction (SFE) and supercritical fluid chromatography (SFC) method was developed for the rapid determination of oleanoic acid and ursolic acid in Chaenomelis Fructus. After optimization of the conditions, the two triterpenoid acids was obtained by SFE using 20% methanol as a modifier at 35°C in 8 min. They were resolved on a Shim-pack UC-X Diol column (4.6 × 150 mm, 3 μm) in 14 min (0 - 10 min, 5 - 10%; 10 - 14 min, 10% methanol in CO 2 ) with a backpressure of 15 MPa at 40°C. The on-line SFE-SFC method could be completed within 40 min (10.79 mg/g dry plant, R s = 2.36), while the ultrasound-assisted extraction and HPLC method required at least 90 min (3.55 mg/g dry plant, R s = 1.92). This on-line SFE-SFC method is powerful to simplify the pre-processing and quantitative analysis of natural products.

  17. Experimental investigation two phase flow in direct methanol fuel cells

    International Nuclear Information System (INIS)

    Mat, M. D.; Kaplan, Y.; Celik, S.; Oeztural, A.

    2007-01-01

    Direct methanol fuel cells (DMFC) have received many attentions specifically for portable electronic applications since it utilize methanol which is in liquid form in atmospheric condition and high energy density of the methanol. Thus it eliminates the storage problem of hydrogen. It also eliminates humidification requirement of polymeric membrane which is a problem in PEM fuel cells. Some electronic companies introduced DMFC prototypes for portable electronic applications. Presence of carbon dioxide gases due to electrochemical reactions in anode makes the problem a two phase problem. A two phase flow may occur at cathode specifically at high current densities due to the excess water. Presence of gas phase in anode region and liquid phase in cathode region prevents diffusion of fuel and oxygen to the reaction sites thus reduces the performance of the system. Uncontrolled pressure buildup in anode region increases methanol crossover through membrane and adversely effect the performance. Two phase flow in both anode and cathode region is very effective in the performance of DMYC system and a detailed understanding of two phase flow for high performance DMFC systems. Although there are many theoretical and experimental studies available on the DMFC systems in the literature, only few studies consider problem as a two-phase flow problem. In this study, an experimental set up is developed and species distributions on system are measured with a gas chromatograph. System performance characteristics (V-I curves) is measured depending on the process parameters (temperature, fuel ad oxidant flow rates, methanol concentration etc)

  18. Methanol Oxidation on Pt3Sn(111) for Direct Methanol Fuel Cells: Methanol Decomposition.

    Science.gov (United States)

    Lu, Xiaoqing; Deng, Zhigang; Guo, Chen; Wang, Weili; Wei, Shuxian; Ng, Siu-Pang; Chen, Xiangfeng; Ding, Ning; Guo, Wenyue; Wu, Chi-Man Lawrence

    2016-05-18

    PtSn alloy, which is a potential material for use in direct methanol fuel cells, can efficiently promote methanol oxidation and alleviate the CO poisoning problem. Herein, methanol decomposition on Pt3Sn(111) was systematically investigated using periodic density functional theory and microkinetic modeling. The geometries and energies of all of the involved species were analyzed, and the decomposition network was mapped out to elaborate the reaction mechanisms. Our results indicated that methanol and formaldehyde were weakly adsorbed, and the other derivatives (CHxOHy, x = 1-3, y = 0-1) were strongly adsorbed and preferred decomposition rather than desorption on Pt3Sn(111). The competitive methanol decomposition started with the initial O-H bond scission followed by successive C-H bond scissions, (i.e., CH3OH → CH3O → CH2O → CHO → CO). The Brønsted-Evans-Polanyi relations and energy barrier decomposition analyses identified the C-H and O-H bond scissions as being more competitive than the C-O bond scission. Microkinetic modeling confirmed that the vast majority of the intermediates and products from methanol decomposition would escape from the Pt3Sn(111) surface at a relatively low temperature, and the coverage of the CO residue decreased with an increase in the temperature and decrease in partial methanol pressure.

  19. Biodiesel production via injection of superheated methanol technology at atmospheric pressure

    International Nuclear Information System (INIS)

    Ang, Gaik Tin; Tan, Kok Tat; Lee, Keat Teong; Mohamed, Abdul Rahman

    2014-01-01

    Highlights: • Non-catalytic superheated methanol for biodiesel production is developed. • Crude Jatropha curcas oil with high FFA can be directly used as oil feedstock. • High content of biodiesel can be produced. • Separation of FAME and glycerol from the sample product is easy. - Abstract: In this high demand of renewable energy market, biodiesel was extensively produced via various catalytic and non-catalytic technologies. Conventional catalytic transesterification for biodiesel production has been shown to have limitation in terms of sensitivity to high water and free fatty acid, complicated separation and purification of biodiesel. In this study, an alternative and innovative approach was carried out via non-catalytic superheated methanol technology to produce biodiesel. Similar to supercritical reaction, the solvent need to be heated beyond the critical temperature but the reactor pressure remained at 0.1 MPa (atmospheric pressure). Transesterification reaction with superheated methanol was carried out at different reaction temperature within the limit of 270–300 °C and at different methanol flow rate ranging from 1 ml/min to 3 ml/min for 4 h. Results obtained showed that the highest biodiesel yield at 71.54% w/w was achieved at reaction temperature 290 °C and methanol flow rate at 2 ml/min with 88.81% w/w FAME content, implying the huge potential of superheated technology in producing FAME

  20. Application of green chemistry techniques to prepare electrocatalysts for direct methanol fuel cells.

    Science.gov (United States)

    Shimizu, Kenichi; Wang, Joanna S; Wai, Chien M

    2010-03-25

    A series of green techniques for synthesizing carbon nanotube-supported platinum nanoparticles and their high electrocatalytic activity toward methanol fuel cell applications are reported. The techniques utilize either the supercritical fluid carbon dioxide or water as a medium for depositing platinum nanoparticles on surfaces of multiwalled or single-walled carbon nanotubes. The catalytic properties of the carbon nanotubes-supported Pt nanoparticle catalysts prepared by four different techniques are compared for anodic oxidation of methanol and cathodic reduction of oxygen using cyclic voltammetry. One technique using galvanic exchange of Pt(2+) in water with zerovalent iron present on the surfaces of as-grown single-walled carbon nanotubes produces a Pt catalyst that shows an unusually high catalytic activity for reduction of oxygen but a negligible activity for oxidation of methanol. This fuel-selective catalyst may have a unique application as a cathode catalyst in methanol fuel cells to alleviate the problems caused by crossover of methanol through the polymer electrolyte membrane.

  1. Towards Overhauser DNP in supercritical CO(2).

    Science.gov (United States)

    van Meerten, S G J; Tayler, M C D; Kentgens, A P M; van Bentum, P J M

    2016-06-01

    Overhauser Dynamic Nuclear Polarization (ODNP) is a well known technique to improve NMR sensitivity in the liquid state, where the large polarization of an electron spin is transferred to a nucleus of interest by cross-relaxation. The efficiency of the Overhauser mechanism for dipolar interactions depends critically on fast local translational dynamics at the timescale of the inverse electron Larmor frequency. The maximum polarization enhancement that can be achieved for (1)H at high magnetic fields benefits from a low viscosity solvent. In this paper we investigate the option to use supercritical CO2 as a solvent for Overhauser DNP. We have investigated the diffusion constants and longitudinal nuclear relaxation rates of toluene in high pressure CO2. The change in (1)H T1 by addition of TEMPO radical was analyzed to determine the Overhauser cross-relaxation in such a mixture, and is compared with calculations based on the Force Free Hard Sphere (FFHS) model. By analyzing the relaxation data within this model we find translational correlation times in the range of 2-4ps, depending on temperature, pressure and toluene concentration. Such short correlation times may be instrumental for future Overhauser DNP applications at high magnetic fields, as are commonly used in NMR. Preliminary DNP experiments have been performed at 3.4T on high pressure superheated water and model systems such as toluene in high pressure CO2. Copyright © 2016 Elsevier Inc. All rights reserved.

  2. Batch extractive distillation for high purity methanol

    International Nuclear Information System (INIS)

    Zhang Weijiang; Ma Sisi

    2006-01-01

    In this paper, the application in chemical industry and microelectronic industry, market status and the present situation of production of high purity methanol at home and abroad were introduced firstly. Purification of industrial methanol for high purity methanol is feasible in china. Batch extractive distillation is the best separation technique for purification of industrial methanol. Dimethyl sulfoxide was better as an extractant. (authors)

  3. European supercritical water cooled reactor

    International Nuclear Information System (INIS)

    Schulenberg, T.; Starflinger, J.; Marsault, P.; Bittermann, D.; Maraczy, C.; Laurien, E.; Lycklama a Nijeholt, J.A.; Anglart, H.; Andreani, M.; Ruzickova, M.; Toivonen, A.

    2011-01-01

    Highlights: → The HPLWR reactor design is an example of a supercritical water cooled reactor. → Cladding material tests have started but materials are not yet satisfactory. → Numerical heat transfer predictions are promising but need further validation. → The research project is most suited for nuclear education and training. - Abstract: The High Performance Light Water Reactor (HPLWR), how the European Supercritical Water Cooled Reactor is called, is a pressure vessel type reactor operated with supercritical water at 25 MPa feedwater pressure and 500 o C average core outlet temperature. It is designed and analyzed by a European consortium of 10 partners and 3 active supporters from 8 Euratom member states in the second phase of the HPLWR project. Most emphasis has been laid on a core with a thermal neutron spectrum, consisting of small fuel assemblies in boxes with 40 fuel pins each and a central water box to improve the neutron moderation despite the low coolant density. Peak cladding temperatures of the fuel rods have been minimized by heating up the coolant in three steps with intermediate coolant mixing. The containment design with its safety and residual heat removal systems is based on the latest boiling water reactor concept, but with different passive high pressure coolant injection systems to cause a forced convection through the core. The design concept of the steam cycle is indicating the envisaged efficiency increase to around 44%. Moreover, it provides the constraints to design the components of the balance of the plant. The project is accompanied by numerical studies of heat transfer of supercritical water in fuel assemblies and by material tests of candidate cladding alloys, performed by the consortium and supported by additional tests of the Joint Research Centre of the European Commission. Besides the scientific and technical progress, the HPLWR project turned out to be most successful in training the young generation of nuclear engineers

  4. The supercritical pomeron in QCD

    International Nuclear Information System (INIS)

    White, A. R.

    1998-01-01

    Deep-inelastic diffractive scaling violations have provided fundamental insight into the QCD pomeron, suggesting a single gluon inner structure rather than that of a perturbative two-gluon bound state. This talk outlines a derivation of a high-energy, transverse momentum cut-off, confining solution of QCD. The pomeron, in first approximation, is a single reggeized gluon plus a ''wee parton'' component that compensates for the color and particle properties of the gluon. This solution corresponds to a super-critical phase of Reggeon Field Theory

  5. Supercritical fluid extraction of uranium

    International Nuclear Information System (INIS)

    Kumar, Pradeep

    2017-01-01

    Uranium being strategic material, its separation and purification is of utmost importance in nuclear industry, for which solvent extraction is being employed. During solvent extraction significant quantity of radioactive liquid waste gets generated which is of environmental concern. In recent decades supercritical fluid extraction (SFE) has emerged as promising alternative to solvent extraction owing to its inherent advantage of reduction in liquid waste generation and simplification of process. In this paper a brief overview of research work carried out so far on SFE of uranium by BARC has been given

  6. Reduction of residual monomer in latex products by enhanced polymerization and extraction in supercritical carbon dioxide

    NARCIS (Netherlands)

    Kemmere, M.F.; Schilt, van M.A.; Cleven, M.H.W.; Herk, van A.M.; Keurentjes, J.T.F.

    2002-01-01

    The redn. of Me methacrylate (MMA) in a PMMA latex was chosen as a representative model system. Pulsed electron beam expts. were performed to study the effect of supercrit. carbon dioxide (scCO2) on the monomer concn. inside the polymer particles during the polymn. reaction. The partitioning

  7. Fast copper extraction from printed circuit boards using supercritical carbon dioxide.

    Science.gov (United States)

    Calgaro, C O; Schlemmer, D F; da Silva, M D C R; Maziero, E V; Tanabe, E H; Bertuol, D A

    2015-11-01

    Technological development and intensive marketing support the growth in demand for electrical and electronic equipment (EEE), for which printed circuit boards (PCBs) are vital components. As these devices become obsolete after short periods, waste PCBs present a problem and require recycling. PCBs are composed of ceramics, polymers, and metals, particularly Cu, which is present in highest percentages. The aim of this study was to develop an innovative method to recover Cu from the PCBs of old mobile phones, obtaining faster reaction kinetics by means of leaching with supercritical CO2 and co-solvents. The PCBs from waste mobile phones were characterized, and evaluation was made of the reaction kinetics during leaching at atmospheric pressure and using supercritical CO2 with H2O2 and H2SO4 as co-solvents. The results showed that the PCBs contained 34.83 wt% of Cu. It was found that the supercritical extraction was 9 times faster, compared to atmospheric pressure extraction. After 20 min of supercritical leaching, approximately 90% of the Cu contained in the PCB was extracted using a 1:20 solid:liquid ratio and 20% of H2O2 and H2SO4 (2.5 M). These results demonstrate the efficiency of the process. Therefore the supercritical CO2 employment in the PCBs recycling is a promising alternative and the CO2 is environmentally acceptable and reusable. Copyright © 2015 Elsevier Ltd. All rights reserved.

  8. The Pore Structure of Direct Methanol Fuel Cell Electrodes

    DEFF Research Database (Denmark)

    Lund, Peter Brilner

    2005-01-01

    The pore structure and morphology of direct methanol fuel cell electrodes are characterized using mercury intrusion porosimetry and scanning electron microscopy. It is found that the pore size distributions of printed primer and catalyst layers are largely dictated by the powders used to make...

  9. Geothermal energy production with supercritical fluids

    Science.gov (United States)

    Brown, Donald W.

    2003-12-30

    There has been invented a method for producing geothermal energy using supercritical fluids for creation of the underground reservoir, production of the geothermal energy, and for heat transport. Underground reservoirs are created by pumping a supercritical fluid such as carbon dioxide into a formation to fracture the rock. Once the reservoir is formed, the same supercritical fluid is allowed to heat up and expand, then is pumped out of the reservoir to transfer the heat to a surface power generating plant or other application.

  10. Supercritical heat transfer phenomena in nuclear system

    International Nuclear Information System (INIS)

    Seo, Kyoung Woo; Kim, Moo Hwan; Anderson, Mark H.; Corradini, Michael L.

    2005-01-01

    A supercritical water (SCW) power cycle has been considered as one of the viable candidates for advanced fission reactor designs. However, the dramatic variation of thermo-physical properties with a modest change of temperature near the pseudo-critical point make existing heat transfer correlations such as the Dittus-Boelter correlation not suitably accurate to calculate the heat transfer in supercritical fluid. Several other correlations have also been suggested but none of them are able to predict the heat transfer over a parameter range, needed for reactor thermal-hydraulics simulation and design. This has prompted additional research to understand the characteristic of supercritical fluid heat transfer

  11. Transesterification of camelina sativa oil with supercritical alcohol mixtures

    International Nuclear Information System (INIS)

    Sun, Yingqiang; Ponnusamy, Sundaravadivelnathan; Muppaneni, Tapaswy; Reddy, Harvind K.; Wang, Jun; Zeng, Zheling; Deng, Shuguang

    2015-01-01

    Highlights: • Transesterification of camelina oil under supercritical methanol/ethanol and 1-butanol mixture conditions. • Chemical composition of fatty acid methyl esters, ethyl esters and butyl esters. • Effect of different alcohol molar ratio on biodiesel yields. • Effect of different alcohol molar ratio on physical properties of biodiesel products. - Abstract: The transesterification of camelina sativa oil with methanol–1-butanol, and ethanol–1-butanol alcohol mixtures under supercritical conditions have been studied in order to maximize biodiesel yield and improve biodiesel quality. The influence of the variation of the molar ratio of methanol–1-butanol and ethanol–1-butanol from 1:0, 3:1, 2:1, 1:1, 1:2, to 0:1 on the yield of free fatty methyl esters/free fatty ethanol esters–free fatty acid butyl esters, the composition of the biodiesel blend mixtures, and the physical properties of the biodiesel have been investigated at the reaction temperature of 290 °C, reaction time of 30 min, and the initial reaction pressure of 500 psi. A maximum yield of 86.14 wt% for free fatty acid methyl esters–free fatty acid butyl esters with the optimum cold property can be obtained at the molar ratio of methanol–1-butanol of 0.5–0.9. Also, a maximum yield of 85.60 wt% for free fatty ethyl esters–free fatty butyl esters with the lowest pour point can be achieved at the molar ratio of ethanol–1-butanol in the range of 0.5–0.7

  12. Challenges of selecting materials for the process of biomass gasification in supercritical water

    Energy Technology Data Exchange (ETDEWEB)

    Boukis, N.; Habicht, W.; Hauer, E.; Dinjus, E. [Karlsruher Institut fuer Technologie (KIT), Karlsruhe (Germany). Inst. fuer Technische Chemie

    2010-07-01

    A new process for the gasification of wet biomass is the reaction in supercritical water. The product is a combustible gas, rich in hydrogen with a high calorific value. The reaction is performed under high temperatures - up to 700 C - and pressures up to 30 MPa. The combination of these physical conditions and the corrosive environment is very demanding for the construction materials of the reactor. Only few alloys exhibit the required mechanical properties, especially the mechanical strength at temperatures higher than 600 C. Ni-Base alloys like alloy 625 can be applied up to a temperature of 700 C and are common materials for application under supercritical water conditions. During gasification experiments with corn silage and other biomasses, corrosion of the reactor material alloy 625 appears. The gasification of an aqueous methanol solution in supercritical water at temperatures up to 600 C and 25 - 30 MPa pressure results in an product gas rich in hydrogen, carbon dioxide and some methane. Alloy 625 shows very low corrosion rates in this environment. It is obvious that the heteroatoms and salts present in biomass cause corrosion of the reactor material. (orig.)

  13. Comparison of supercritical fluid and Soxhlet extractions for the quantification of hydrocarbons from Euphorbia macroclada.

    Science.gov (United States)

    Ozcan, Adnan; Ozcan, Asiye Safa

    2004-10-08

    This study compares conventional Soxhlet extraction and analytical scale supercritical fluid extraction (SFE) for their yields in extracting of hydrocarbons from arid-land plant Euphorbia macroclada. The plant material was firstly sequentially extracted with supercritical carbon dioxide, modified with 10% methanol (v/v) in the optimum conditions that is a pressure of 400atm and a temperature of 50 degrees C and then it was sonicated in methylene chloride for an additional 4h. E. macroclada was secondly extracted by using a Soxhlet apparatus at 30 degrees C for 8h in methylene chloride. The validated SFE was then compared to the extraction yield of E. macroclada with a Soxhlet extraction by using the Student's t-test at the 95% confidence level. All of extracts were fractionated with silica-gel in a glass column to get better hydrocarbon yields. Thus, the highest hydrocarbons yield from E. macroclada was achieved with SFE (5.8%) when it compared with Soxhlet extractions (1.1%). Gas chromatography (GC) analysis was performed to determine the quantitative hydrocarbons from plant material. The greatest quantitative hydrocarbon recovery from GC was obtained by supercritical carbon dioxide extract (0.6mgg(-1)).

  14. A flow-through column electrolytic cell for supercritical fluid chromatography.

    Science.gov (United States)

    Yamamoto, Kazuhiro; Ueki, Tatsuya; Higuchi, Naoyuki; Takahashi, Kouji; Kotani, Akira; Hakamata, Hideki

    2017-10-01

    A novel flow-through column electrolytic cell was proposed as a detector to obtain current signals for supercritical fluid chromatography. The electrochemical cell consisted of two electrodes and its holder, and a working and a counter electrode were fabricated from 192 carbon strings, which were composed of 400 carbon fibers of 10 μm in diameter filled into a heat-shrinkable tube. These electrodes were placed in the center of a holder made from polyether ether ketone blocks and they were separated by polytetrafluoroethylene membrane filters. To evaluate the sensitivity of this cell, a standard solution of ferrocene was injected into the supercritical fluid chromatography system connected to the electrolytic cell. The ferrocene was eluted through a silica gel column using a mixture of a mobile phase of supercritical CO 2 and a modifier of methanol containing ammonium acetate. The current peak area of ferrocene correlated to the ferrocene concentration in the range of 10-400 μmol/L (r = 0.999). Moreover, the limit of detection on the column estimated from a signal-to-noise ratio of 3 was 9.8  × 10 -13  mol. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. A first-principles study of Pt–Ni bimetallic cluster adsorption on the anatase TiO{sub 2} (1 0 1) surface: Probing electron effect of Ni in TiO{sub 2} (1 0 1)-bimetallic cluster (Pt–Ni) on the adsorption and dissociation of methanol

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Feila, E-mail: liufeila@u.washington.edu [College of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400044 (China); Department of Materials Science and Engineering, University of Washington, Seattle, WA 98195 (United States); Xiao, Peng, E-mail: xiaopeng@cqu.edu.cn [College of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400044 (China); Uchaker, Evan, E-mail: uchaker@u.washington.edu [Department of Materials Science and Engineering, University of Washington, Seattle, WA 98195 (United States); He, Huichao, E-mail: hehuichao985@gmail.com [College of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400044 (China); Zhou, Ming, E-mail: Zhoumingcqu2007@163.com [College of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400044 (China); Zhou, Xin, E-mail: zhoux@hit.edu.cn [State Key Laboratory of Urban Water Resource and Environment, Institute of Theoretical and Simulation Chemistry, Academy of Fundamental and Interdisciplinary Sciences, Harbin Institute of Technology, Harbin 150080 (China); Zhang, Yunhuai, E-mail: xp2031@163.com [College of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400044 (China)

    2014-10-01

    Graphical abstract: - Highlights: • Condensed Fukui function is used to predict the regioselectivity of clusters. • Pt–Ni alloy and TiO{sub 2} can effectively oxidize methanol compared with pure Pt. • The methanol dehydrogenation over Pt{sub 3}Ni/TiO{sub 2} is an optimal reaction pathway. • The alloying of Ni can effectively alleviate CO poisoning. - Abstract: A density functional theory (DFT) based method in conjunction with the projector augmented wave and pseudopotential methods have been applied to investigate the adsorption of Pt{sub 4} and Pt{sub 3}Ni on the anatase TiO{sub 2} (1 0 1) surface. Two stable Pt{sub 3}Ni adsorptions with considerable adsorption energies on the anatase TiO{sub 2} (1 0 1) surface were identified. Analysis of the partial density (PDOS) of states and Bader charge suggest that the electronic structure of Pt is modified by Ni due to the electron transfer from Ni to Pt atoms in the Pt{sub 3}Ni clusters. The 2cO (3cO)-PtNi-5cTi conformation of the adsorbed Pt{sub 3}Ni on the anatase TiO{sub 2} (1 0 1) surface provides a more feasible model for electron injection through the Pt{sub 3}Ni/TiO{sub 2} interface. The reactivity of Pt{sub 3}Ni/TiO{sub 2} is superior to Pt{sub 4}/TiO{sub 2} and effectively manifests itself in the eased decomposition of O-H bonds derived by methanol and alleviative CO adsorption.

  16. Fuels Combustion Research: Supercritical Fuel Pyrolysis

    National Research Council Canada - National Science Library

    Glassman, Irvin

    2001-01-01

    .... The focus during the subject period was directed to understanding the pyrolysis and combustion of endothermic fuels under subcritical conditions and the pyrolysis of these fuels under supercritical conditions...

  17. Fuels Combustion Research: Supercritical Fuel Pyrolysis

    National Research Council Canada - National Science Library

    Glassman, Irvin

    2000-01-01

    .... The focus during the subject period was directed to understanding the pyrolysis and combustion of endothermic fuels under subcritical conditions and the pyrolysis of these fuels under supercritical conditions...

  18. Charting the Landscape of Supercritical String Theory

    International Nuclear Information System (INIS)

    Hellerman, Simeon; Swanson, Ian

    2007-01-01

    Special solutions of string theory in supercritical dimensions can interpolate in time between theories with different numbers of spacetime dimensions and different amounts of world sheet supersymmetry. These solutions connect supercritical string theories to the more familiar string duality web in ten dimensions and provide a precise link between supersymmetric and purely bosonic string theories. Dimension quenching and c duality appear to be natural concepts in string theory, giving rise to large networks of interconnected theories

  19. Supercritical solvent extraction of oil sand bitumen

    Science.gov (United States)

    Imanbayev, Ye. I.; Ongarbayev, Ye. K.; Tileuberdi, Ye.; Mansurov, Z. A.; Golovko, A. K.; Rudyk, S.

    2017-08-01

    The supercritical solvent extraction of bitumen from oil sand studied with organic solvents. The experiments were performed in autoclave reactor at temperature above 255 °C and pressure 29 atm with stirring for 6 h. The reaction resulted in the formation of coke products with mineral part of oil sands. The remaining products separated into SARA fractions. The properties of the obtained products were studied. The supercritical solvent extraction significantly upgraded extracted natural bitumen.

  20. Supercritical fields and bald black holes

    Energy Technology Data Exchange (ETDEWEB)

    Irvine, J M

    1975-01-01

    The instability of a many-fermion ground state against particle-hole excitations is reviewed and the existence of supercritical electromagnetic and strong interaction fields is briefly discussed. The nature of associated phase changes and in particular the change in conservation laws which accompanies the phase changes is outlined. Finally, the supercritical gravitational field is considered and weight given to the argument that ''black holes have no hair.''

  1. Methanol electro-oxidation and direct methanol fuel cell using Pt/Rh and Pt/Ru/Rh alloy catalysts

    International Nuclear Information System (INIS)

    Choi, Jong-Ho; Park, Kyung-Won; Park, In-Su; Nam, Woo-Hyun; Sung, Yung-Eun

    2004-01-01

    Pt-based binary or ternary catalysts containing Rh for use as anodes in direct methanol fuel cells (DMFC) were synthesized by borohydride reduction method combined with freeze-drying. The resulting catalysts had a specific surface area of approximately 65-75 m 2 /g. X-ray diffraction (XRD) patterns indicated that the catalysts were well alloyed and the average size of alloy catalysts was confirmed by transmission electron microscopy (TEM). The Pt/Rh (2:1) and Pt/Ru/Rh (5:4:1) alloy catalysts showed better catalytic activities for methanol electro-oxidation than Pt or Pt/Ru (1:1), respectively

  2. Sub- and supercritical jet disintegration

    Science.gov (United States)

    DeSouza, Shaun; Segal, Corin

    2017-04-01

    Shadowgraph visualization and Planar Laser Induced Fluorescence (PLIF) are applied to single orifice injection in the same facility and same fluid conditions to analyze sub- to supercritical jet disintegration and mixing. The comparison includes jet disintegration and lateral spreading angle. The results indicate that the shadowgraph data are in agreement with previous visualization studies but differ from the PLIF results that provided quantitative measurement of central jet plane density and density gradients. The study further evaluated the effect of thermodynamic conditions on droplet production and quantified droplet size and distribution. The results indicate an increase in the normalized drop diameter and a decrease in the droplet population with increasing chamber temperatures. Droplet size and distribution were found to be independent of chamber pressure.

  3. Supercritical Water Oxidation Program (SCWOP)

    International Nuclear Information System (INIS)

    1994-02-01

    Purpose of SCWOP is to develop and demonstrate supercritical water oxidation as a viable technology for treating DOE hazardous and mixed wastes and to coordinate SCWO research, development, demonstration, testing, and evaluation activities. The process involves bringing together organic waste, water, and an oxidant (air, O 2 , etc.) to temperatures and pressures above water's critical point (374 C, 22.1 MPa); organic destruction is >99.99% efficient, and the resulting effluents (mostly water, CO 2 ) are relatively benign. Pilot-scale (300--500 gallons/day) SCWO units are to be constructed and demonstrated. Two phases will be conducted: hazardous waste pilot plant demonstration and mixed waste pilot demonstration. Contacts for further information and for getting involved are given

  4. Supercritical fluid reverse micelle separation

    Science.gov (United States)

    Fulton, J.L.; Smith, R.D.

    1993-11-30

    A method of separating solute material from a polar fluid in a first polar fluid phase is provided. The method comprises combining a polar fluid, a second fluid that is a gas at standard temperature and pressure and has a critical density, and a surfactant. The solute material is dissolved in the polar fluid to define the first polar fluid phase. The combined polar and second fluids, surfactant, and solute material dissolved in the polar fluid is maintained under near critical or supercritical temperature and pressure conditions such that the density of the second fluid exceeds the critical density thereof. In this way, a reverse micelle system defining a reverse micelle solvent is formed which comprises a continuous phase in the second fluid and a plurality of reverse micelles dispersed in the continuous phase. The solute material is dissolved in the polar fluid and is in chemical equilibrium with the reverse micelles. The first polar fluid phase and the continuous phase are immiscible. The reverse micelles each comprise a dynamic aggregate of surfactant molecules surrounding a core of the polar fluid. The reverse micelle solvent has a polar fluid-to-surfactant molar ratio W, which can vary over a range having a maximum ratio W[sub o] that determines the maximum size of the reverse micelles. The maximum ratio W[sub o] of the reverse micelle solvent is then varied, and the solute material from the first polar fluid phase is transported into the reverse micelles in the continuous phase at an extraction efficiency determined by the critical or supercritical conditions. 27 figures.

  5. Transesterification of soybean oil with methanol and acetic acid at lower reaction severity under subcritical conditions

    International Nuclear Information System (INIS)

    Go, Alchris Woo; Sutanto, Sylviana; NguyenThi, Bich Thuyen; Cabatingan, Luis K.; Ismadji, Suryadi; Ju, Yi-Hsu

    2014-01-01

    Highlights: • (trans)Esterification of oils under subcritical conditions. • Acetic acid as catalyst and co-solvent in biodiesel production. • Influence of reactor hydrodynamic (loading and stirring) on FAME yield. • High methyl ester yield can be obtained at less severe reaction conditions. - Abstract: Soybean oil (56–80 g) was reacted with methanol (40–106 mL) to produce fatty acid methyl ester in the presence of 1–6% acetic acid under subcritical condition at 250 °C. Stirring and loading of the reaction system affected the yield and severity of the process. The presence of acetic acid improved the yield of FAME from 32.1% to 89.5% at a methanol to oil molar ratio of 20 mL/g. Acetic acid was found to act strongly as an acid catalyst and to some extent improved the solubility between oil and methanol. Reaction pressure higher than the supercritical pressure of methanol (7.85 MPa) was not required to achieve high FAME yield (89.5–94.8%) in short time (30–60 min)

  6. Supercritical CO2 Extracts and Volatile Oil of Basil (Ocimum basilicum L. Comparison with Conventional Methods

    Directory of Open Access Journals (Sweden)

    José Coelho

    2018-03-01

    Full Text Available Interest in new products from aromatic plants as medical and nutritional compounds is increasing. The aim of this work was to apply different extraction methods, including the use of supercritical carbon dioxide extraction, and to test the antioxidant activity of basil (Ocimum basilicum L. extracts. In vitro efficacy assessments were performed using enzymatic assays. Essential oil obtained by hydrodistillation and volatile oil obtained from supercritical fluid extraction were analyzed by gas chromatography to quantify components. The total phenolic content in the extracts ranged from 35.5 ± 2.9 to 85.3 ± 8.6 mg of gallic acid equivalents and the total flavonoid content ranged from 35.5 ± 2.9 to 93.3 ± 3.9 micromole catechin equivalents per gram of dry weight of extract. All the extracts showed an antioxidant activity with 2,2-diphenyl-1-picrylhydrazyl (DPPH, 2,2-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid (ABTS, and the reducing power test. Extracts obtained from methanol had a higher antioxidant capacity per the DPPH test results (IC50 = 3.05 ± 0.36 mg/mL and the reducing power test assay 306.8 ± 21.8 μmol of trolox equivalents per gram of extract (TE/g compared with ethanolic or supercritical fluid extracts. However, using the ABTS assay, the extract obtained by supercritical fluid extraction had a higher antioxidant capacity with an IC50 of 1.74 ± 0.05 mg/mL. Finally, the examined extracts showed practically no acetylcholinesterase (AChE inhibitory capacity and a slight inhibitory activity against tyrosinase.

  7. Organization of Genes Required for the Oxidation of Methanol to Formaldehyde in Three Type II Methylotrophs

    Science.gov (United States)

    Bastien, C.; Machlin, S.; Zhang, Y.; Donaldson, K.; Hanson, R. S.

    1989-01-01

    Restriction maps of genes required for the synthesis of active methanol dehydrogenase in Methylobacterium organophilum XX and Methylobacterium sp. strain AM1 have been completed and compared. In these two species of pink-pigmented, type II methylotrophs, 15 genes were identified that were required for the expression of methanol dehydrogenase activity. None of these genes were required for the synthesis of the prosthetic group of methanol dehydrogenase, pyrroloquinoline quinone. The structural gene required for the synthesis of cytochrome cL, an electron acceptor uniquely required for methanol dehydrogenase, and the genes encoding small basic peptides that copurified with methanol dehydrogenases were closely linked to the methanol dehydrogenase structural genes. A cloned 22-kilobase DNA insert from Methylsporovibrio methanica 81Z, an obligate type II methanotroph, complemented mutants that contained lesions in four genes closely linked to the methanol dehydrogenase structural genes. The methanol dehydrogenase and cytochrome cL structural genes were found to be transcribed independently in M. organophilum XX. Only two of the genes required for methanol dehydrogenase synthesis in this bacterium were found to be cotranscribed. PMID:16348074

  8. Towards a methanol economy based on homogeneous catalysis: methanol to H2 and CO2 to methanol

    DEFF Research Database (Denmark)

    Alberico, E.; Nielsen, Martin

    2015-01-01

    The possibility to implement both the exhaustive dehydrogenation of aqueous methanol to hydrogen and CO2 and the reverse reaction, the hydrogenation of CO2 to methanol and water, may pave the way to a methanol based economy as part of a promising renewable energy system. Recently, homogeneous...

  9. Analysis of new psychoactive substances in human urine by ultra-high performance supercritical fluid and liquid chromatography: Validation and comparison.

    Science.gov (United States)

    Borovcová, Lucie; Pauk, Volodymyr; Lemr, Karel

    2018-05-01

    New psychoactive substances represent serious social and health problem as tens of new compounds are detected in Europe annually. They often show structural proximity or even isomerism, which complicates their analysis. Two methods based on ultra high performance supercritical fluid chromatography and ultra high performance liquid chromatography with mass spectrometric detection were validated and compared. A simple dilute-filter-and-shoot protocol utilizing propan-2-ol or methanol for supercritical fluid or liquid chromatography, respectively, was proposed to detect and quantify 15 cathinones and phenethylamines in human urine. Both methods offered fast separation (chromatography. Limits of detection in urine ranged from 0.01 to 2.3 ng/mL, except for cathinone (5 ng/mL) in supercritical fluid chromatography. Nevertheless, this technique distinguished all analytes including four pairs of isomers, while liquid chromatography was unable to resolve fluoromethcathinone regioisomers. Concerning matrix effects and recoveries, supercritical fluid chromatography produced more uniform results for different compounds and at different concentration levels. This work demonstrates the performance and reliability of supercritical fluid chromatography and corroborates its applicability as an alternative tool for analysis of new psychoactive substances in biological matrixes. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. New catalysts for miniaturized methanol fuel cells

    DEFF Research Database (Denmark)

    Pedersen, Christoffer Mølleskov

    The methanol fuel cell is an interesting energy technology, capable of converting the chemical energy of methanol directly into electricity. The technology is specifically attractive for small mobile applications such as laptops, smartphones, tablets etc. since it offers almost instantaneously...

  11. Selective Synthesis of Manganese/Silicon Complexes in Supercritical Water

    Directory of Open Access Journals (Sweden)

    Jiancheng Wang

    2014-01-01

    Full Text Available A series of manganese salts (Mn(NO32, MnCl2, MnSO4, and Mn(Ac2 and silicon materials (silica sand, silica sol, and tetraethyl orthosilicate were used to synthesize Mn/Si complexes in supercritical water using a tube reactor. X-ray diffraction (XRD, X-ray photoelectron spectrometer (XPS, transmission electron microscopy (TEM, and scanning electron microscopy (SEM were employed to characterize the structure and morphology of the solid products. It was found that MnO2, Mn2O3, and Mn2SiO4 could be obtained in supercritical water at 673 K in 5 minutes. The roles of both anions of manganese salts and silicon species in the formation of manganese silicon complexes were discussed. The inorganic manganese salt with the oxyacid radical could be easily decomposed to produce MnO2/SiO2 and Mn2O3/SiO2. It is interesting to found that Mn(Ac2 can react with various types of silicon to produce Mn2SiO4. The hydroxyl groups of the SiO2 surface from different silicon sources enhance the reactivity of SiO2.

  12. Purification, crystallization and preliminary X-ray crystallographic analysis of a methanol dehydrogenase from the marine bacterium Methylophaga aminisulfidivorans MPT

    International Nuclear Information System (INIS)

    Choi, Jin Myung; Kim, Hee Gon; Kim, Jeong-Sun; Youn, Hyung-Seop; Eom, Soo Hyun; Yu, Sung-Lim; Kim, Si Wouk; Lee, Sung Haeng

    2011-01-01

    In order to obtain molecular insights into the methanol-oxidizing system of M. aminisulfidivorans, a native heterotetrameric α 2 β 2 methanol dehydrogenase complex was directly purified from M. aminisulfidivorans MP T grown in the presence of methanol and crystallized. Methylophaga aminisulfidivorans MP T is a marine methylotrophic bacterium that utilizes C 1 compounds such as methanol as a carbon and energy source. The released electron from oxidation flows through a methanol-oxidizing system (MOX) consisting of a series of electron-transfer proteins encoded by the mox operon. One of the key enzymes in the pathway is methanol dehydrogenase (MDH), which contains the prosthetic group pyrroloquinoline quinone (PQQ) and converts methanol to formaldehyde in the periplasm by transferring two electrons from the oxidation of one methanol molecule to the electron acceptor cytochrome c L . In order to obtain molecular insights into the oxidation mechanism, a native heterotetrameric α 2 β 2 MDH complex was directly purified from M. aminisulfidivorans MP T grown in the presence of methanol and crystallized. The crystal diffracted to 1.7 Å resolution and belonged to the monoclinic space group P2 1 (unit-cell parameters a = 63.9, b = 109.5, c = 95.6 Å, β = 100.5°). The asymmetric unit of the crystal contained one heterotetrameric complex, with a calculated Matthews coefficient of 2.24 Å 3 Da −1 and a solvent content of 45.0%

  13. Operation and Performance of the Supercritical Fluids Reactor (SFR)

    National Research Council Canada - National Science Library

    Hanush, R

    1996-01-01

    The Supercritical Fluids Reactor (SFR) at Sandia National Laboratories, CA has been developed to examine and solve engineering, process, and fundamental chemistry issues regarding the development of supercritical water oxidation (SCWO...

  14. Catalyst retention in continuous flow with supercritical carbon dioxide

    NARCIS (Netherlands)

    Stouten, S.C.; Noel, T.; Wang, Q.; Hessel, V.

    2014-01-01

    This review discusses the retention of organometallic catalysts in continuous flow processes utilizing supercritical carbon dioxide. Due to its innovative properties, supercritical carbon dioxide offers interesting possibilities for process intensification. As a result of safety and cost

  15. NMR studies on graphite-methanol system

    International Nuclear Information System (INIS)

    El-Akkad, T.M.

    1977-01-01

    The nuclear magnetic relaxation times for protons of methanol on graphite have been studied. The perpendicular and the transversal magnetization as a function of temperature were measured. The results show that the presence of graphite slowed down the methanol movement compared with that in the pure alcohol, and that the methanol molecules are attached to the graphite surface via methyl groups. (author)

  16. Sorption of methanol in alkali exchange zeolites

    NARCIS (Netherlands)

    Rep, M.; Rep, M.; Corma, Avelino; Palomares, A.E.; Palomares gimeno, A.E.; van Ommen, J.G.; Lefferts, Leonardus; Lercher, J.A.

    2000-01-01

    Metal cation methanol sorption complexes in MFI (ZSM5), MOR and X have been studied by in situ i.r. spectroscopy in order to understand the nature of interactions of methanol in the molecular sieve pores. The results show that (a) a freely vibrating hydroxy and methyl group of methanol exist on

  17. The fate of methanol in anaerobic bioreactors

    NARCIS (Netherlands)

    Florencio, L.

    1994-01-01

    Methanol is an important component of certain industrial wastewaters. In anaerobic environments, methanol can be utilized by methanogens and acetogens. In wastewater treatment plants, the conversion of methanol into methane is preferred because this conversion is responsible for chemical

  18. Methanol decomposition and oxidation on Ir(111)

    NARCIS (Netherlands)

    Weststrate, C.J.; Ludwig, W.; Bakker, J.W.; Gluhoi, A.C.; Nieuwenhuys, B.E.

    2007-01-01

    The adsorption, decompn., and oxidn. of methanol (CH3OH) has been studied on Ir(111) using temp.-programmed desorption and high-energy resoln. fast XPS. Mol. methanol desorption from a methanol-satd. surface at low temp. shows three desorption peaks, around 150 K (alpha ), around 170 K (beta 1), and

  19. Supercritical fluid technology: concepts and pharmaceutical applications.

    Science.gov (United States)

    Deshpande, Praful Balavant; Kumar, G Aravind; Kumar, Averineni Ranjith; Shavi, Gopal Venkatesh; Karthik, Arumugam; Reddy, Meka Sreenivasa; Udupa, Nayanabhirama

    2011-01-01

    In light of environmental apprehension, supercritical fluid technology (SFT) exhibits excellent opportunities to accomplish key objectives in the drug delivery sector. Supercritical fluid extraction using carbon dioxide (CO(2)) has been recognized as a green technology. It is a clean and versatile solvent with gas-like diffusivity and liquid-like density in the supercritical phase, which has provided an excellent alternative to the use of chemical solvents. The present commentary provides an overview of different techniques using supercritical fluids and their future opportunity for the drug delivery industry. Some of the emerging applications of SFT in pharmaceuticals, such as particle design, drug solubilization, inclusion complex, polymer impregnation, polymorphism, drug extraction process, and analysis, are also covered in this review. The data collection methods are based on the recent literature related to drug delivery systems using SFT platforms. SFT has become a much more versatile and environmentally attractive technology that can handle a variety of complicated problems in pharmaceuticals. This cutting-edge technology is growing predominantly to surrogate conventional unit operations in relevance to the pharmaceutical production process. Supercritical fluid technology has recently drawn attention in the field of pharmaceuticals. It is a distinct conception that utilizes the solvent properties of supercritical fluids above their critical temperature and pressure, where they exhibit both liquid-like and gas-like properties, which can enable many pharmaceutical applications. For example, the liquid-like properties provide benefits in extraction processes of organic solvents or impurities, drug solubilization, and polymer plasticization, and the gas-like features facilitate mass transfer processes. It has become a much more versatile and environmentally attractive technology that can handle a variety of complicated problems in pharmaceuticals. This review is

  20. Portable DMFC system with methanol sensor-less control

    Energy Technology Data Exchange (ETDEWEB)

    Chen, C.Y.; Liu, D.H.; Huang, C.L.; Chang, C.L. [Institute of Nuclear Energy Research (INER), No. 1000, Wunhua Rd., Jiaan Village, Longtan Township, Taoyuan County 32546 (China)

    2007-05-15

    This work develops a prototype 20 W portable DMFC by system integration of stack, condenser, methanol sensor-less control and start-up characteristics. The effects of these key components and control schemes on the performance are also discussed. To expedite the use of portable DMFC in electronic applications, the system utilizes a novel methanol sensor-less control method, providing improved fuel efficiency, durability, miniaturization and cost reduction. The operating characteristics of the DMFC stack are applied to control the fuel ejection time and period, enabling the system to continue operating even when the MEAs of the stack are deteriorated. The portable system is also designed with several features including water balance and quick start-up (in 5 min). Notably, the proposed system using methanol sensor-less control with injection of pure methanol can power the DVD player and notebook PC. The system specific energy and energy density following three days of operation are 362 Wh kg{sup -1} and 335 Wh L{sup -1}, respectively, which are better than those of lithium batteries ({proportional_to}150 Wh kg{sup -1} and {proportional_to}250 Wh L{sup -}). This good energy storage feature demonstrates that the portable DMFC is likely to be valuable in computer, communication and consumer electronic (3C) markets. (author)

  1. Oxidation behavior of steels and Alloy 800 in supercritical water

    International Nuclear Information System (INIS)

    Olmedo, A.M.; Bordoni, R.; Dominguez, G.; Alvarez, M.G.

    2011-01-01

    The oxidation behavior of a ferritic-martensitic steel T91 and a martensitic steel AISI 403 up to 750 h, and of AISI 316L and Alloy 800 up to 336 h in deaerated supercritical water, 450ºC-25 MPa, was investigated in this paper. After exposure up to 750 h, the weight gain data, for steels T91 and AISI 403, was fitted by ∆W=k t n , were n are similar for both steels and k is a little higher for T91. The oxide films grown in the steels were characterized using gravimetry, scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM/EDS) and X-ray diffraction. The films were adherent and exhibited a low porosity. For this low oxygen content supercritical water exposure, the oxide scale exhibited a typical duplex structure, in which the scale is composed of an outer iron oxide layer of magnetite (Fe 3 O 4 ) and an inner iron/chromium oxide layer of a non-stoichiometric iron chromite (Fe,Cr) 3 O 4 . Preliminary results, with AISI 316L and Alloy 800, for two exposure periods (168 and 336 h), are also reported. The morphology shown for the oxide films grown on both materials up to 336 h of oxidation in supercritical water, resembles that of a duplex layer film like that shown by stainless steels and Alloy 800 oxide films grown in a in a high temperature and pressure (220-350ºC) of a primary or secondary coolant of a plant. (author) [es

  2. Supercritical CO₂assisted extraction and LC-MS identification of picroside I and picroside II from Picrorhiza kurroa.

    Science.gov (United States)

    Patil, Ajit A; Sachin, Bhusari S; Shinde, Devanand B; Wakte, Pravin S

    2013-02-01

    Picroside I and picroside II have been studied intensively because of their pharmacological actions and clinical applications. Numerous methods have been reported for extracting picroside I and picroside II from Picrorrhiza. kurroa rhizomes. This is the first report of picroside I and picroside II extraction using the supercritical carbon dioxide assisted extraction technique. To develop supercritical carbon dioxide assisted extraction and LC-MS identification of picroside I and picroside II from the Picrorrhiza kurroa Royle rhizomes. Surface response methodology based on 3³ fractional factorial design was used to extract picroside I and picroside II from P. kurroa rhizomes. The effects of various process factors, namely temperature (40-80°C), pressure (25-35 MPa) and co-solvent (methanol) concentration (0-10% v/v) on extraction yield of the two compounds were evaluated. The picroside I and picroside II contents were determined using validated LC-MS methodology. The maximum yield of picroside I (32.502 ± 1.131 mg/g) and picroside II (9.717 ± 0.382 mg/g) was obtained at the 10% v/v co-solvent concentration, 40°C temperature and 30 MPa pressure. The conventional Soxhlet assisted methanol extract of P. kurroa powder resulted in 36.743 ± 1.75 and 11.251 ± 0.54 mg/g yield of picroside I and picroside II, respectively. Variation of concentration and extraction time showed a significant effect on the picroside I and picroside II yield. Supercritical carbon dioxide assisted extraction using methanol as a co-solvent is an efficient and environmentally sustainable method for extracting picroside I and picroside II from P. kurroa rhizomes. Copyright © 2012 John Wiley & Sons, Ltd.

  3. Optimization of microwave-assisted extraction and supercritical fluid extraction of carbamate pesticides in soil by experimental design methodology.

    Science.gov (United States)

    Sun, Lei; Lee, Hian Kee

    2003-10-03

    Orthogonal array design (OAD) was applied for the first time to optimize microwave-assisted extraction (MAE) and supercritical fluid extraction (SFE) conditions for the analysis of four carbamates (propoxur, propham, methiocarb, chlorpropham) from soil. The theory and methodology of a new OA16 (4(4)) matrix derived from a OA16 (2(15)) matrix were developed during the MAE optimization. An analysis of variance technique was employed as the data analysis strategy in this study. Determinations of analytes were completed using high-performance liquid chromatography (HPLC) with UV detection. Four carbamates were successfully extracted from soil with recoveries ranging from 85 to 105% with good reproducibility (approximately 4.9% RSD) under the optimum MAE conditions: 30 ml methanol, 80 degrees C extraction temperature, and 6-min microwave heating. An OA8 (2(7)) matrix was employed for the SFE optimization. The average recoveries and RSD of the analytes from spiked soil by SFE were 92 and 5.5%, respectively except for propham (66.3+/-7.9%), under the following conditions: heating for 30 min at 60 degrees C under supercritical CO2 at 300 kg/cm2 modified with 10% (v/v) methanol. The composition of the supercritical fluid was demonstrated to be a crucial factor in the extraction. The addition of a small volume (10%) of methanol to CO2 greatly enhanced the recoveries of carbamates. A comparison of MAE with SFE was also conducted. The results indicated that >85% average recoveries were obtained by both optimized extraction techniques, and slightly higher recoveries of three carbamates (propoxur, propham and methiocarb) were achieved using MAE. SFE showed slightly higher recovery for chlorpropham (93 vs. 87% for MAE). The effects of time-aged soil on the extraction of analytes were examined and the results obtained by both methods were also compared.

  4. Pressure drop and friction factor correlations of supercritical flow

    International Nuclear Information System (INIS)

    Fang Xiande; Xu Yu; Su Xianghui; Shi Rongrong

    2012-01-01

    Highlights: ► Survey and evaluation of friction factor models for supercritical flow. ► Survey of experimental study of supercritical flow. ► New correlation of friction factor for supercritical flow. - Abstract: The determination of the in-tube friction pressure drop under supercritical conditions is important to the design, analysis and simulation of transcritical cycles of air conditioning and heat pump systems, nuclear reactor cooling systems and some other systems. A number of correlations for supercritical friction factors have been proposed. Their accuracy and applicability should be examined. This paper provides a comprehensive survey of experimental investigations into the pressure drop of supercritical flow in the past decade and a comparative study of supercritical friction factor correlations. Our analysis shows that none of the existing correlations is completely satisfactory, that there are contradictions between the existing experimental results and thus more elaborate experiments are needed, and that the tube roughness should be considered. A new friction factor correlation for supercritical tube flow is proposed based on 390 experimental data from the available literature, including 263 data of supercritical R410A cooling, 45 data of supercritical R404A cooling, 64 data of supercritical carbon dioxide (CO 2 ) cooling and 18 data of supercritical R22 heating. Compared with the best existing model, the new correlation increases the accuracy by more than 10%.

  5. Advanced Supercritical Carbon Dioxide Brayton Cycle Development

    Energy Technology Data Exchange (ETDEWEB)

    Anderson, Mark [Univ. of Wisconsin, Madison, WI (United States); Sienicki, James [Argonne National Lab. (ANL), Argonne, IL (United States); Moisseytsev, Anton [Argonne National Lab. (ANL), Argonne, IL (United States); Nellis, Gregory [Univ. of Wisconsin, Madison, WI (United States); Klein, Sanford [Univ. of Wisconsin, Madison, WI (United States)

    2015-10-21

    Fluids operating in the supercritical state have promising characteristics for future high efficiency power cycles. In order to develop power cycles using supercritical fluids, it is necessary to understand the flow characteristics of fluids under both supercritical and two-phase conditions. In this study, a Computational Fluid Dynamic (CFD) methodology was developed for supercritical fluids flowing through complex geometries. A real fluid property module was implemented to provide properties for different supercritical fluids. However, in each simulation case, there is only one species of fluid. As a result, the fluid property module provides properties for either supercritical CO2 (S-CO2) or supercritical water (SCW). The Homogeneous Equilibrium Model (HEM) was employed to model the two-phase flow. HEM assumes two phases have same velocity, pressure, and temperature, making it only applicable for the dilute dispersed two-phase flow situation. Three example geometries, including orifices, labyrinth seals, and valves, were used to validate this methodology with experimental data. For the first geometry, S-CO2 and SCW flowing through orifices were simulated and compared with experimental data. The maximum difference between the mass flow rate predictions and experimental measurements is less than 5%. This is a significant improvement as previous works can only guarantee 10% error. In this research, several efforts were made to help this improvement. First, an accurate real fluid module was used to provide properties. Second, the upstream condition was determined by pressure and density, which determines supercritical states more precise than using pressure and temperature. For the second geometry, the flow through labyrinth seals was studied. After a successful validation, parametric studies were performed to study geometric effects on the leakage rate. Based on these parametric studies, an optimum design strategy for the see

  6. Characteristics of PVdF copolymer/Nafion blend membrane for direct methanol fuel cell (DMFC)

    International Nuclear Information System (INIS)

    Cho, Ki-Yun; Eom, Ji-Yong; Jung, Ho-Young; Choi, Nam-Soon; Lee, Yong Min; Park, Jung-Ki; Choi, Jong-Ho; Park, Kyung-Won; Sung, Yung-Eun

    2004-01-01

    For direct methanol fuel cell, blends of vinylidene fluoride-hexafluoropropylene copolymer (P(VdF-co-HFP)) and Nafion were prepared the different equivalent weight of Nafion. The investigations of the blend morphology were performed by means of permeability test, uptake measurement, differential-scanning calorimetry (DSC), and scanning electron microscopy. In the blend membranes, many pores were created as the content of Nafion in blend increased. Then, the methanol uptake was sharply increased. But the methanol permeability was not sharply increased because the methanol permeation through blend membranes is diffusion-controlled process. The methanol permeability of N10 (low equivalent weight) series was similar to that of N11 series (high equivalent weight). The proton conductivity of N10 series was around one and a half times higher than that of N11 series. The cell performance of the blend was much enhanced when the equivalent weight of Nafion was 1000

  7. Theoretical models for supercritical fluid extraction.

    Science.gov (United States)

    Huang, Zhen; Shi, Xiao-Han; Jiang, Wei-Juan

    2012-08-10

    For the proper design of supercritical fluid extraction processes, it is essential to have a sound knowledge of the mass transfer mechanism of the extraction process and the appropriate mathematical representation. In this paper, the advances and applications of kinetic models for describing supercritical fluid extraction from various solid matrices have been presented. The theoretical models overviewed here include the hot ball diffusion, broken and intact cell, shrinking core and some relatively simple models. Mathematical representations of these models have been in detail interpreted as well as their assumptions, parameter identifications and application examples. Extraction process of the analyte solute from the solid matrix by means of supercritical fluid includes the dissolution of the analyte from the solid, the analyte diffusion in the matrix and its transport to the bulk supercritical fluid. Mechanisms involved in a mass transfer model are discussed in terms of external mass transfer resistance, internal mass transfer resistance, solute-solid interactions and axial dispersion. The correlations of the external mass transfer coefficient and axial dispersion coefficient with certain dimensionless numbers are also discussed. Among these models, the broken and intact cell model seems to be the most relevant mathematical model as it is able to provide realistic description of the plant material structure for better understanding the mass-transfer kinetics and thus it has been widely employed for modeling supercritical fluid extraction of natural matters. Copyright © 2012 Elsevier B.V. All rights reserved.

  8. Supercritical Fluid Chromatographic Separation of Dimethylpolysiloxane Polymer

    Energy Technology Data Exchange (ETDEWEB)

    Pyo, Dong Jin; Lim, Chang Hyun [Kangwon National University, Chuncheon (Korea, Republic of)

    2005-02-15

    Water was used as a polar modifier and a μ-porasil column as a saturator column. The μ-porasil column was inserted between the pump outlet and the injection valve. During the passage of the supercritical fluid mobile phase through the silica column, a polar modifier (water) can be dissolved in the pressurized supercritical fluid. Dimethylpolysiloxane polymer has been known as more polar polymer than polystyrene polymer. Dimethylpolysiloxane polymer has never been separated using water modified mobile phase. In this paper, using a μ-porasil column as a saturator column, excellent supercritical fluid chromatograms of dimethylpolysiloxane oligomers were obtained. The use of compressed (dense) gases and supercritical fluids as chromatographic mobile phases in conjunction with liquid chromatographic (LC)-type packed columns was first reported by Klesper et al. in 1962. During its relatively short history, supercritical fluid chromatography (SFC) has become an attractive alternative to GC and LC in certain industrially important applications. SFC gives the advantage of high efficiency and allows the analysis of nonvolatile or thermally labile mixtures.

  9. Supercritical Fluid Chromatographic Separation of Dimethylpolysiloxane Polymer

    International Nuclear Information System (INIS)

    Pyo, Dong Jin; Lim, Chang Hyun

    2005-01-01

    Water was used as a polar modifier and a μ-porasil column as a saturator column. The μ-porasil column was inserted between the pump outlet and the injection valve. During the passage of the supercritical fluid mobile phase through the silica column, a polar modifier (water) can be dissolved in the pressurized supercritical fluid. Dimethylpolysiloxane polymer has been known as more polar polymer than polystyrene polymer. Dimethylpolysiloxane polymer has never been separated using water modified mobile phase. In this paper, using a μ-porasil column as a saturator column, excellent supercritical fluid chromatograms of dimethylpolysiloxane oligomers were obtained. The use of compressed (dense) gases and supercritical fluids as chromatographic mobile phases in conjunction with liquid chromatographic (LC)-type packed columns was first reported by Klesper et al. in 1962. During its relatively short history, supercritical fluid chromatography (SFC) has become an attractive alternative to GC and LC in certain industrially important applications. SFC gives the advantage of high efficiency and allows the analysis of nonvolatile or thermally labile mixtures

  10. Corrosion in Supercritical carbon Dioxide: Materials, Environmental Purity, Surface Treatments, and Flow Issues

    Energy Technology Data Exchange (ETDEWEB)

    Sridharan, Kumar; Anderson, Mark

    2013-12-10

    separately to high purity CO{sub 2}. Task 3: Evaluation of surface treatments on the corrosion performance of alloys in supercritical CO{sub 2}: Surface treatments can be very beneficial in improving corrosion resistance. Shot peening and yttrium and aluminum surface treatments will be investigated. Shot peening refines the surface grain sizes and promotes protective Cr-oxide layer formation. Both yttrium and aluminum form highly stable oxide layers (Y{sub 2}O{sub 3} and Al{sub 2}O{sub 3}), which can get incorporated in the growing Fe-oxide layer to form an impervious complex oxide to enhance corrosion resistance. Task 4: Study of flow-assisted corrosion of select alloys in supercritical CO{sub 2} under a selected set of test conditions: To study the effects of flow-assisted corrosion, tests will be conducted in a supercritical CO{sub 2} flow loop. An existing facility used for supercritical water flow studies at the proposing university will be modified for use in this task. The system is capable of flow velocities up to 10 m/s and can operate at temperatures and pressures of up to 650°C and 20 MPa, respectively. All above tasks will be performed in conjunction with detailed materials characterization and analysis using scanning electron microscopy/energy dispersive spectroscopy (SEM-EDS), x-ray diffraction (XRD), Auger electron spectroscopy (AES) techniques, and weight change measurements. Inlet and outlet gas compositions will be monitored using gas chromatography-mass spectrometry (GCMS).

  11. Metabolism of methanol in acetogenic bacteria

    International Nuclear Information System (INIS)

    Ivey, D.K.W.

    1987-01-01

    Acetogens can grown on methanol in the presence of a cosubstrate that is more oxidized than methanol. Three mol of acetate is formed from 4 mol methanol and 2 mol CO 2 . One mol of methanol is oxidized to CO 2 . The levels of the tetrahydrofolate enzymes, carbon monoxide dehydrogenase, and corrinoids indicate the presence of the acetyl CoA pathway when growing on methanol. The acetyl-CoA pathway of acetate synthesis as presently understood does not include methanol as a substrate. It is demonstrated that methanol is oxidized to formaldehyde and then to formate by a methanol dehydrogenase. It is also possible that the methyl group of methanol is transferred directly to either a corrinoid-type enzyme, or tetrahydrofolate. When cells of C. thermoautotrophicum are grown on 14 CO 2 , acetate becomes labeled in both carbons with a ratio 14 CH 3 / 14 COOH of 0.7. In addition, methanol gets labeled. When cells are grown on 14 CH 3 OH, label appears in both acetate carbons with a ratio of 3.3, and also appears in CO 2 . Thus methanol is preferentially incorporated into the methyl group of acetate, whereas CO 2 is the preferred source of the carboxyl carbon

  12. Triboluminescence and associated decomposition of solid methanol

    International Nuclear Information System (INIS)

    Trout, G.J.; Moore, D.E.; Hawke, J.G.

    1975-01-01

    The decomposition is initiated by the cooling of solid methanol through the β → α transiRon at 157.8K, producing the gases hydrogen, carbon monoxide, and methane. The passage through this lambda transition causes the breakup of large crystals of β-methanol into crystallites of α-methanol and is accompanied by light emission as well as decomposition. This triboluminescence is accompanied by, and apparently produced by, electrical discharges through methanol vapor in the vicinity of the solid. The potential differences needed to produce the electrical breakdown of the methanol vapor apparently arise from the disruption of the long hydrogen bonded chains of methanol molecules present in crystalline methanol. Charge separation following crystal deformation is a characteristic of substances which exhibit gas discharge triboluminescence; solid methanol has been found to emit such luminescence when mechanically deformed in the absence of the β → α transition The decomposition products are not produced directly by the breaking up of the solid methanol but from the vapor phase methanol by the electrical discharges. That gas phase decomposition does occur was confirmed by observing that the vapors of C 2 H 5 OH, CH 3 OD, and CD 3 OD decompose on being admitted to a vessel containing methanol undergoing the β → α phase transition. (U.S.)

  13. The methanol industry's missed opportunities

    International Nuclear Information System (INIS)

    Stokes, C.A.

    1995-01-01

    Throughout its history the methanol industry has been backward in research and development and in industry cooperation on public image and regulatory matters. It has been extremely reticent as to the virtue of its product for new uses, especially for motor fuel. While this is perhaps understandable looking back, it is inexcusable looking forward. The industry needs to cooperate on a worldwide basis in research and market development, on the one hand, and in image-building and political influence, on the other, staying, of course, within the US and European and other regional antitrust regulations. Unless the industry develops the motor fuel market, and especially the exciting new approach through fuel cell operated EVs, to siphon off incremental capacity and keep plants running at 90% or more of capacity, it will continue to live in a price roller-coaster climate. A few low-cost producers will do reasonably well and the rest will just get along or drop out here and there along the way, as in the past. Having come so far from such a humble beginning, it is a shame not to realize the full potential that is clearly there: a potential to nearly double sales dollars without new plants and to produce from a plentiful resource, at least for the next half-century, all the methanol that can be imagined to be needed. Beyond that the industry can turn to renewable energy--the sun--via biomass growth, to make their product. In so doing, it can perhaps apply methanol as a plant growth stimulant, in effect making the product fully self-sustainable. The world needs to know what methanol can do to provide--economically and reliably--the things upon which a better life rests

  14. Methanol from biomass: A technoeconomic analysis

    International Nuclear Information System (INIS)

    Stevens, D.J.

    1991-01-01

    Biomass-derived methanol offers significant potential as an alternative transportation fuel. Methanol is cleaner burning and has a lower flame temperature than gasoline. These characteristics can result in lower carbon monoxide and nitrogen oxide emissions when methanol is used as a fuel. Methanol produced from biomass offers potential advantages over that from other sources. When produced from biomass which is subsequently regrown, methanol does not contribute net emissions of carbon dioxide, a greenhouse gas, to the atmosphere. The introduction of alternative fuels will likely be driven by a number of political and economic decisions. The ability of biomass to compete with other resources will be determined in part by the economics of the production systems. In this paper, recent technoeconomic analyses of biomass-methanol systems are presented. The results are compared with methanol production from coal and natural gas

  15. Development of an Accelerated Methodology to Study Degradation of Materials in Supercritical Water for Application in High Temperature Power Plants

    Science.gov (United States)

    Rodriguez, David

    The decreasing supply of fossil fuel sources, coupled with the increasing concentration of green house gases has placed enormous pressure to maximize the efficiency of power generation. Increasing the outlet temperature of these power plants will result in an increase in operating efficiency. By employing supercritical water as the coolant in thermal power plants (nuclear reactors and coal power plants), the plant efficiency can be increased to 50%, compared to traditional reactors which currently operate at 33%. The goal of this dissertation is to establish techniques to characterize the mechanical properties and corrosion behavior of materials exposed to supercritical water. Traditionally, these tests have been long term exposure tests spanning months. The specific goal of this dissertation is to develop a methodology for accelerated estimation of corrosion rates in supercritical water that can be sued as a screening tool to select materials for long term testing. In this study, traditional methods were used to understand the degradation of materials in supercritical water and establish a point of comparison to the first electrochemical studies performed in supercritical water. Materials studied included austenitic steels (stainless steel 304, stainless steel 316 and Nitronic 50) and nickel based alloys (Inconel 625 and 718). Surface chemistry of the oxide layer was characterized using scanning electron microscopy, X-ray diffraction, FT-IR, Raman and X-ray photoelectron spectroscopies. Stainless steel 304 was subjected to constant tensile load creep tests in water at a pressure of 27 MPa and at temperatures of 200 °C, 315 °C and supercritical water at 450 °C for 24 hours. It was determined that the creep rate for stainless steel 304 exposed to supercritical water would be unacceptable for use in service. It was observed that the formation of hematite was favored in subcritical temperatures, while magnetite was formed in the supercritical region. Corrosion of

  16. Enhancing power cycle efficiency for a supercritical Brayton cycle power system using tunable supercritical gas mixtures

    Science.gov (United States)

    Wright, Steven A.; Pickard, Paul S.; Vernon, Milton E.; Radel, Ross F.

    2017-08-29

    Various technologies pertaining to tuning composition of a fluid mixture in a supercritical Brayton cycle power generation system are described herein. Compounds, such as Alkanes, are selectively added or removed from an operating fluid of the supercritical Brayton cycle power generation system to cause the critical temperature of the fluid to move up or down, depending upon environmental conditions. As efficiency of the supercritical Brayton cycle power generation system is substantially optimized when heat is rejected near the critical temperature of the fluid, dynamically modifying the critical temperature of the fluid based upon sensed environmental conditions improves efficiency of such a system.

  17. Driving Interconnected Networks to Supercriticality

    Directory of Open Access Journals (Sweden)

    Filippo Radicchi

    2014-04-01

    Full Text Available Networks in the real world do not exist as isolated entities, but they are often part of more complicated structures composed of many interconnected network layers. Recent studies have shown that such mutual dependence makes real networked systems potentially exposed to atypical structural and dynamical behaviors, and thus there is an urgent necessity to better understand the mechanisms at the basis of these anomalies. Previous research has mainly focused on the emergence of atypical properties in relation to the moments of the intra- and interlayer degree distributions. In this paper, we show that an additional ingredient plays a fundamental role for the possible scenario that an interconnected network can face: the correlation between intra- and interlayer degrees. For sufficiently high amounts of correlation, an interconnected network can be tuned, by varying the moments of the intra- and interlayer degree distributions, in distinct topological and dynamical regimes. When instead the correlation between intra- and interlayer degrees is lower than a critical value, the system enters in a supercritical regime where dynamical and topological phases are no longer distinguishable.

  18. Supercritical waste oxidation pump investigation

    International Nuclear Information System (INIS)

    Thurston, G.; Garcia, K.

    1993-02-01

    This report investigates the pumping techniques and pumping equipment that would be appropriate for a 5,000 gallon per day supercritical water oxidation waste disposal facility. The pumps must boost water, waste, and additives from atmospheric pressure to approximately 27.6 MPa (4,000 psia). The required flow ranges from 10 gpm to less than 0.1 gpm. For the higher flows, many commercial piston pumps are available. These pumps have packing and check-valves that will require periodic maintenance; probably at 2 to 6 month intervals. Several commercial diaphragm pumps were also discovered that could pump the higher flow rates. Diaphragm pumps have the advantage of not requiring dynamic seals. For the lower flows associated with the waste and additive materials, commercial diaphragm pumps. are available. Difficult to pump materials that are sticky, radioactive, or contain solids, could be injected with an accumulator using an inert gas as the driving mechanism. The information presented in this report serves as a spring board for trade studies and the development of equipment specifications

  19. Supercritical carbon dioxide hop extraction

    Directory of Open Access Journals (Sweden)

    Pfaf-Šovljanski Ivana I.

    2005-01-01

    Full Text Available The hop of Magnum cultivar was extracted using supercritical carbon dioxide (SFE-as extractant. Extraction was carried out in the two steps: the first one being carried out at 150 bar and 40°C for 2.5 h (Extract A, and the second was the extraction of the same hop sample at 300 bar and 40°C for 2.5 h (Extract B. Extraction kinetics of the system hop-SFE-CO2 was investigated. Two of four most common compounds of hop aroma (α-humulene and β-caryophyllene were detected in Extract A. Isomerised α-acids and β-acids were detected too. a-Acid content in Extract B was high (that means it is a bitter variety of hop. Mathematical modeling using empirical model characteristic time model and simple single sphere model has been performed on Magnum cultivar extraction experimental results. Characteristic time model equations, best fitted experimental results. Empirical model equation, fitted results well, while simple single sphere model equation poorly approximated the results.

  20. Supercritical fluid extraction of hops

    Directory of Open Access Journals (Sweden)

    ZORAN ZEKOVIC

    2007-01-01

    Full Text Available Five cultivars of hop were extracted by the method of supercritical fluid extraction using carbon dioxide (SFE–CO2 as extractant. The extraction (50 g of hop sample using a CO2 flow rate of 97.725 L/h was done in the two steps: 1. extraction at 150 bar and 40°C for 2.5 h (sample of series A was obtained and, after that, the same sample of hop was extracted in the second step: 2. extraction at 300 bar and 40 °C for 2.5 h (sample of series B was obtained. The Magnum cultivar was chosen for the investigation of the extraction kinetics. For the qualitative and quantitative analysis of the obtained hop extracts, the GC-MS method was used. Two of four themost common compounds of hop aroma (a-humulene and b-caryophyllene were detected in samples of series A. In addition, isomerized a-acids and a high content of b-acids were detected. The a-acids content in the samples of series B was the highest in the extract of the Magnum cultivar (it is a bitter variety of hop. The low contents of a-acids in all the other hop samples resulted in extracts with low a-acids content, i.e., that contents were under the prescribed a-acids content.

  1. Enantioseparation of novel chiral sulfoxides on chlorinated polysaccharide stationary phases in supercritical fluid chromatography.

    Science.gov (United States)

    West, Caroline; Konjaria, Mari-Luiza; Shashviashvili, Natia; Lemasson, Elise; Bonnet, Pascal; Kakava, Rusudan; Volonterio, Alessandro; Chankvetadze, Bezhan

    2017-05-26

    Asymmetric sulfoxides is a particular case of chirality that may be found in natural as well as synthetic products. Twenty-four original molecules containing a sulfur atom as a centre of chirality were analyzed in supercritical fluid chromatography on seven polysaccharide-based chiral stationary phases (CSP) with carbon dioxide - methanol mobile phases. While all the tested CSP provided enantioseparation for a large part of the racemates, chlorinated cellulosic phases proved to be both highly retentive and highly enantioselective towards these species. Favourable structural features were determined by careful comparison of the enantioseparation of the probe molecules. Molecular modelling studies indicate that U-shaped (folded) conformations were most favorable to achieve high enantioresolution on these CSP, while linear (extended) conformations were not so clearly discriminated. For a subset of these species adopting different conformations, a broad range of mobile phase compositions, ranging from 20 to 100% methanol in carbon dioxide, were investigated. While retention decreased continuously in this range, enantioseparation varied in a non-monotonous fashion. Abrupt changes in the tendency curves of retention and selectivity were observed when methanol proportion reaches about 60%, suggesting that a change in the conformation of the analytes and/or chiral selector is occurring at this point. Copyright © 2017 Elsevier B.V. All rights reserved.

  2. Heat Transfer Phenomena of Supercritical Fluids

    Energy Technology Data Exchange (ETDEWEB)

    Krau, Carmen Isabella; Kuhn, Dietmar; Schulenberg, Thomas [Forschungszentrum Karlsruhe, Institute for Nuclear and Energy Technologies, 76021 Karlsruhe (Germany)

    2008-07-01

    In concepts for supercritical water cooled reactors, the reactor core is cooled and moderated by water at supercritical pressures. The significant temperature dependence of the fluid properties of water requires an exact knowledge of the heat transfer mechanism to avoid fuel pin damages. Near the pseudo-critical point a deterioration of heat transfer might happen. Processes, that take place in this case, are not fully understood and are due to be examined systematically. In this paper a general overview on the properties of supercritical water is given, experimental observations of different authors will be reviewed in order to identify heat transfer phenomena and onset of occurrence. The conceptional design of a test rig to investigate heat transfer in the boundary layer will be discussed. Both, water and carbon dioxide, may serve as operating fluids. The loop, including instrumentation and safety devices, is shown and suitable measuring methods are described. (authors)

  3. Upgrading of bitumen using supercritical water

    Energy Technology Data Exchange (ETDEWEB)

    Kayukawa, T. [JGC Corp., Ibaraki (Japan)

    2009-07-01

    This presentation outlined the technical and economic aspects of thermal cracking by supercritical water. Supercritical water (SCW) is a commonly used method for upgrading heavy oil to produce pipeline-transportable oil from high-viscous bitumen. The process uses water and does not require hydrogen nor catalysts. Pre-heated bitumen and water enter a vertical reactor with flows of counter current at the supercritical point of water. The upgraded synthetic crude oil (SCO) and pitch are obtained from the top of the reactor when the bitumen is thermally cracked. Bench-scale studies have shown that Canadian oil sands bitumen can be converted to 80 volume per cent of SCO and 20 volume per cent of pitch. The SCO has satisfied Canadian pipeline specifications in terms of API gravity and kinetic viscosity. The kinetic viscosity of the pitch has also satisfied boiler fuel specifications. tabs., figs.

  4. Supercritical water decontamination of town gas soil

    International Nuclear Information System (INIS)

    Kocher, B.S.; Azzam, F.O.; Lee, S.

    1994-01-01

    Town gas sites represent a large environmental problem that exists in more than 2,000 sites across North America alone. The major contaminants in town gas sods are polycyclic aromatic hydrocarbons (PAHs). These are stable compounds that migrate deep into the soil and are traditionally very difficult to remove by conventional remediation processes. Supercritical fluids offer enhanced solvating properties along with reduced mass transfer resistances that make them ideal for removing compounds that are difficult or impossible to remove by conventional processes. Supercritical water is ideal for removing PAHs and other hydrocarbons from soil due to its high solvating power towards most hydrocarbon species. Supercritical water was investigated for its ability to remediate two different town gas sods containing from 3--20 wt% contamination. The sod was remediated in a 300-cc semi-continuous system to a more environmentally acceptable level

  5. Application of polythiophene to methanol vapor detection: an ab initio study.

    Science.gov (United States)

    Shokuhi Rad, Ali

    2015-11-01

    The interaction of methanol with terthiophene (3PT; a model of polythiophene) was investigated using density functional theory (DFT) at the BLYP-D3/6-31+G(d,p) level of theory. The computed density of states (DOS) pointed to considerable orbital hybridization upon the interaction of methanol with 3PT. Natural population analysis (NPA) was used to determine the charge distribution as well as the net charge transfer within the 3PT-methanol system, and thus to assess the sensing ability of terthiophene. The computed dipole moment revealed that the dielectric μ D changes upon the interaction of methanol with 3PT. Using calculated changes in the HOMO-LUMO energy gap, it was deduced that the electronic properties of 3PT are sensitive to the interaction of 3PT with methanol. After full energy relaxation, the interaction energy of methanol with 3PT in the most stable configuration was calculated to be -16.4 (counterpoise-corrected energy: -13.5) kJ mol(-1), providing proof that methanol is physisorbed by 3PT. Graphical Abstract Adsorption of methanol on polythiophene.

  6. Preparation of Cefquinome Nanoparticles by Using the Supercritical Antisolvent Process

    Directory of Open Access Journals (Sweden)

    Xiao Kefeng

    2015-01-01

    Full Text Available The supercritical antisolvent process was used successfully to prepare nanoparticles of cefquinome. These particles were observed by scanning electron microscope (SEM and their average diameter was measured by laser particle size analyzer. In the experiments, dimethyl sulfoxide (DMSO was selected as solvent to dissolve cefquinome sulfate. It was confirmed by orthogonal experiments that the concentration of solution was the primary factor in this process followed by feeding speed of solution, precipitation pressure, and precipitation temperature. Moreover, the optimal conditions of preparing nanoparticles of cefquinome by supercritical antisolvent process were that solution concentration was 100 mg/mL, solution flow speed was 1.5 mL/min, operating pressure was 13 Mpa, and operating temperature was 33°C. Confirmatory experiment was conducted under this condition. It was found that the appearance of particles was flakes and the average diameter of particles was 0.71 microns. Finally, influence law of individual factor on particle size was investigated by univariate analysis.

  7. Recovery of cobalt from spent lithium-ion batteries using supercritical carbon dioxide extraction.

    Science.gov (United States)

    Bertuol, Daniel A; Machado, Caroline M; Silva, Mariana L; Calgaro, Camila O; Dotto, Guilherme L; Tanabe, Eduardo H

    2016-05-01

    Continuing technological development decreases the useful lifetime of electronic equipment, resulting in the generation of waste and the need for new and more efficient recycling processes. The objective of this work is to study the effectiveness of supercritical fluids for the leaching of cobalt contained in lithium-ion batteries (LIBs). For comparative purposes, leaching tests are performed with supercritical CO2 and co-solvents, as well as under conventional conditions. In both cases, sulfuric acid and H2O2 are used as reagents. The solution obtained from the supercritical leaching is processed using electrowinning in order to recover the cobalt. The results show that at atmospheric pressure, cobalt leaching is favored by increasing the amount of H2O2 (from 0 to 8% v/v). The use of supercritical conditions enable extraction of more than 95wt% of the cobalt, with reduction of the reaction time from 60min (the time employed in leaching at atmospheric pressure) to 5min, and a reduction in the concentration of H2O2 required from 8 to 4% (v/v). Electrowinning using a leach solution achieve a current efficiency of 96% and a deposit with cobalt concentration of 99.5wt%. Copyright © 2016 Elsevier Ltd. All rights reserved.

  8. Endogenous Methanol Regulates Mammalian Gene Activity

    Science.gov (United States)

    Komarova, Tatiana V.; Petrunia, Igor V.; Shindyapina, Anastasia V.; Silachev, Denis N.; Sheshukova, Ekaterina V.; Kiryanov, Gleb I.; Dorokhov, Yuri L.

    2014-01-01

    We recently showed that methanol emitted by wounded plants might function as a signaling molecule for plant-to-plant and plant-to-animal communications. In mammals, methanol is considered a poison because the enzyme alcohol dehydrogenase (ADH) converts methanol into toxic formaldehyde. However, the detection of methanol in the blood and exhaled air of healthy volunteers suggests that methanol may be a chemical with specific functions rather than a metabolic waste product. Using a genome-wide analysis of the mouse brain, we demonstrated that an increase in blood methanol concentration led to a change in the accumulation of mRNAs from genes primarily involved in detoxification processes and regulation of the alcohol/aldehyde dehydrogenases gene cluster. To test the role of ADH in the maintenance of low methanol concentration in the plasma, we used the specific ADH inhibitor 4-methylpyrazole (4-MP) and showed that intraperitoneal administration of 4-MP resulted in a significant increase in the plasma methanol, ethanol and formaldehyde concentrations. Removal of the intestine significantly decreased the rate of methanol addition to the plasma and suggested that the gut flora may be involved in the endogenous production of methanol. ADH in the liver was identified as the main enzyme for metabolizing methanol because an increase in the methanol and ethanol contents in the liver homogenate was observed after 4-MP administration into the portal vein. Liver mRNA quantification showed changes in the accumulation of mRNAs from genes involved in cell signalling and detoxification processes. We hypothesized that endogenous methanol acts as a regulator of homeostasis by controlling the mRNA synthesis. PMID:24587296

  9. Endogenous methanol regulates mammalian gene activity.

    Directory of Open Access Journals (Sweden)

    Tatiana V Komarova

    Full Text Available We recently showed that methanol emitted by wounded plants might function as a signaling molecule for plant-to-plant and plant-to-animal communications. In mammals, methanol is considered a poison because the enzyme alcohol dehydrogenase (ADH converts methanol into toxic formaldehyde. However, the detection of methanol in the blood and exhaled air of healthy volunteers suggests that methanol may be a chemical with specific functions rather than a metabolic waste product. Using a genome-wide analysis of the mouse brain, we demonstrated that an increase in blood methanol concentration led to a change in the accumulation of mRNAs from genes primarily involved in detoxification processes and regulation of the alcohol/aldehyde dehydrogenases gene cluster. To test the role of ADH in the maintenance of low methanol concentration in the plasma, we used the specific ADH inhibitor 4-methylpyrazole (4-MP and showed that intraperitoneal administration of 4-MP resulted in a significant increase in the plasma methanol, ethanol and formaldehyde concentrations. Removal of the intestine significantly decreased the rate of methanol addition to the plasma and suggested that the gut flora may be involved in the endogenous production of methanol. ADH in the liver was identified as the main enzyme for metabolizing methanol because an increase in the methanol and ethanol contents in the liver homogenate was observed after 4-MP administration into the portal vein. Liver mRNA quantification showed changes in the accumulation of mRNAs from genes involved in cell signalling and detoxification processes. We hypothesized that endogenous methanol acts as a regulator of homeostasis by controlling the mRNA synthesis.

  10. Solid catalyzed isoparaffin alkylation at supercritical fluid and near-supercritical fluid conditions

    Science.gov (United States)

    Ginosar, Daniel M.; Fox, Robert V.; Kong, Peter C.

    2000-01-01

    This invention relates to an improved method for the alkylation reaction of isoparaffins with olefins over solid catalysts including contacting a mixture of an isoparaffin, an olefin and a phase-modifying material with a solid acid catalyst member under alkylation conversion conditions at either supercritical fluid, or near-supercritical fluid conditions, at a temperature and a pressure relative to the critical temperature(T.sub.c) and the critical pressure(P.sub.c) of the reaction mixture. The phase-modifying phase-modifying material is employed to promote the reaction's achievement of either a supercritical fluid state or a near-supercritical state while simultaneously allowing for decreased reaction temperature and longer catalyst life.

  11. Hydrogen Bonding Interaction between Atmospheric Gaseous Amides and Methanol

    Directory of Open Access Journals (Sweden)

    Hailiang Zhao

    2016-12-01

    Full Text Available Amides are important atmospheric organic–nitrogen compounds. Hydrogen bonded complexes of methanol (MeOH with amides (formamide, N-methylformamide, N,N-dimethylformamide, acetamide, N-methylacetamide and N,N-dimethylacetamide have been investigated. The carbonyl oxygen of the amides behaves as a hydrogen bond acceptor and the NH group of the amides acts as a hydrogen bond donor. The dominant hydrogen bonding interaction occurs between the carbonyl oxygen and the OH group of methanol as well as the interaction between the NH group of amides and the oxygen of methanol. However, the hydrogen bonds between the CH group and the carbonyl oxygen or the oxygen of methanol are also important for the overall stability of the complexes. Comparable red shifts of the C=O, NH- and OH-stretching transitions were found in these MeOH–amide complexes with considerable intensity enhancement. Topological analysis shows that the electron density at the bond critical points of the complexes fall in the range of hydrogen bonding criteria, and the Laplacian of charge density of the O–H∙∙∙O hydrogen bond slightly exceeds the upper value of the Laplacian criteria. The energy decomposition analysis further suggests that the hydrogen bonding interaction energies can be mainly attributed to the electrostatic, exchange and dispersion components.

  12. Hydrogen Bonding Interaction between Atmospheric Gaseous Amides and Methanol.

    Science.gov (United States)

    Zhao, Hailiang; Tang, Shanshan; Xu, Xiang; Du, Lin

    2016-12-30

    Amides are important atmospheric organic-nitrogen compounds. Hydrogen bonded complexes of methanol (MeOH) with amides (formamide, N -methylformamide, N , N -dimethylformamide, acetamide, N -methylacetamide and N , N -dimethylacetamide) have been investigated. The carbonyl oxygen of the amides behaves as a hydrogen bond acceptor and the NH group of the amides acts as a hydrogen bond donor. The dominant hydrogen bonding interaction occurs between the carbonyl oxygen and the OH group of methanol as well as the interaction between the NH group of amides and the oxygen of methanol. However, the hydrogen bonds between the CH group and the carbonyl oxygen or the oxygen of methanol are also important for the overall stability of the complexes. Comparable red shifts of the C=O, NH- and OH-stretching transitions were found in these MeOH-amide complexes with considerable intensity enhancement. Topological analysis shows that the electron density at the bond critical points of the complexes fall in the range of hydrogen bonding criteria, and the Laplacian of charge density of the O-H∙∙∙O hydrogen bond slightly exceeds the upper value of the Laplacian criteria. The energy decomposition analysis further suggests that the hydrogen bonding interaction energies can be mainly attributed to the electrostatic, exchange and dispersion components.

  13. Design and Operation of an Electrochemical Methanol Concentration Sensor for Direct Methanol Fuel Cell Systems

    Science.gov (United States)

    Narayanan, S. R.; Valdez, T. I.; Chun, W.

    2000-01-01

    The development of a 150-Watt packaged power source based on liquid feed direct methanol fuel cells is being pursued currently at the Jet propulsion Laboratory for defense applications. In our studies we find that the concentration of methanol in the fuel circulation loop affects the electrical performance and efficiency the direct methanol fuel cell systems significantly. The practical operation of direct methanol fuel cell systems, therefore, requires accurate monitoring and control of methanol concentration. The present paper reports on the principle and demonstration of an in-house developed electrochemical sensor suitable for direct methanol fuel cell systems.

  14. Recent Studies on Methanol Crossover in Liquid-Feed Direct Methanol Fuel Cells

    Science.gov (United States)

    Valdez, T. I.; Narayanan, S. R.

    2000-01-01

    In this work, the effects of methanol crossover and airflow rates on the cathode potential of an operating direct methanol fuel cell are explored. Techniques for quantifying methanol crossover in a fuel cell and for separating the electrical performance of each electrode in a fuel cell are discussed. The effect of methanol concentration on cathode potential has been determined to be significant. The cathode is found to be mass transfer limited when operating on low flow rate air and high concentrations of methanol. Improvements in cathode structure and operation at low methanol concentration have been shown to result in improved cell performance.

  15. Theoretical Study of the NMR Chemical Shift of Xe in Supercritical Condition

    DEFF Research Database (Denmark)

    Lacerda Junior, Evanildo Gomes; Sauer, Stephan P. A.; Mikkelsen, Kurt Valentin

    2018-01-01

    In this work we investigate the level of theory necessary for reproducing the non-linear variation of the 129Xe nuclear magnetic resonance (NMR) chemical shift with the density of Xe in supercritical conditions. In detail we study how the 129Xe chemical shift depends under these conditions...... on electron correlation, relativistic and many-body effects. The latter are included using a sequential-QM/MM methodology, in which a classical MD simulation is performed first and the chemical shift is then obtained as an average of quantum calculations of 250 MD snapshots conformations carried out for Xen...... this approach we obtain very good agreement with the experimental data, showing that the chemical shift of 129Xe in supercritical conditions is very well described by cluster calculations at the HF level, with small contributions from relativistic and electron correlation effects....

  16. Methods of conditioning direct methanol fuel cells

    Science.gov (United States)

    Rice, Cynthia; Ren, Xiaoming; Gottesfeld, Shimshon

    2005-11-08

    Methods for conditioning the membrane electrode assembly of a direct methanol fuel cell ("DMFC") are disclosed. In a first method, an electrical current of polarity opposite to that used in a functioning direct methanol fuel cell is passed through the anode surface of the membrane electrode assembly. In a second method, methanol is supplied to an anode surface of the membrane electrode assembly, allowed to cross over the polymer electrolyte membrane of the membrane electrode assembly to a cathode surface of the membrane electrode assembly, and an electrical current of polarity opposite to that in a functioning direct methanol fuel cell is drawn through the membrane electrode assembly, wherein methanol is oxidized at the cathode surface of the membrane electrode assembly while the catalyst on the anode surface is reduced. Surface oxides on the direct methanol fuel cell anode catalyst of the membrane electrode assembly are thereby reduced.

  17. Relating Direct Methanol Fuel Cell Performance to Measurements in a Liquid Half Cell

    DEFF Research Database (Denmark)

    Pedersen, Christoffer Mølleskov; Tynelius, Oskar; Lund-Olesen, Torsten

    2015-01-01

    Direct methanol fuel cells (DMFC) could act as a replacement for batteries in low power electronics. For instance, micro—DMFC’s could be used to power hearing instruments[1]. The power output of a DMFC is limited by the sluggish kinetics of both the methanol oxidation reaction (MOR) on the anode ...... Cells Bull. 2012 (2012) 12–16. doi:10.1016/S1464-2859(12)70367-X....

  18. Supercritical synthesis and in situ deposition of PbS nanocrystals with oleic acid passivation for quantum dot solar cells

    Energy Technology Data Exchange (ETDEWEB)

    Tavakoli, M.M. [Department of Materials Science and Engineering, Sharif University of Technology, 14588 Tehran (Iran, Islamic Republic of); Simchi, A., E-mail: simchi@sharif.edu [Department of Materials Science and Engineering, Sharif University of Technology, 14588 Tehran (Iran, Islamic Republic of); Institute for Nanoscience and Nanotechnology, Sharif University of Technology, 14588 Tehran (Iran, Islamic Republic of); Aashuri, H. [Department of Materials Science and Engineering, Sharif University of Technology, 14588 Tehran (Iran, Islamic Republic of)

    2015-04-15

    Colloidal quantum dot solar cells have recently attracted significant attention due to their low-processing cost and surging photovoltaic performance. In this paper, a novel, reproducible, and simple solution-based process based on supercritical fluid toluene is presented for in situ growth and deposition PbS nanocrystals with oleic-acid passivation. A lead precursor containing sulfur was mixed with oleic acid in toluene and processed in a supercritical fluid condition at different temperatures of 140, 270 and 330 °C for 20 min. The quantum dots were deposited on a fluorine-doped tin oxide glass substrate inside the supercritical reactor. Transmission electron microscopy, X-ray diffraction, absorption and dynamic light scattering showed that the nanocrystals processed at the supercritical condition (330 °C) are fully crystalline with a narrow size distribution of ∼3 nm with an absorption wavelength of 915 nm (bandgap of 1.3 eV). Fourier transform infrared spectroscopy indicated that the PbS quantum dots are passivated by oleic acid molecules during the growth. Photovoltaic characteristics of Schottky junction solar cells showed an improvement over devices prepared by spin-coating. - Highlights: • Supercritical fluid processing and in situ deposition of PbS QDs are presented. • The prepared nanocrystals are mono-dispersed with an optical bandgap of 1.3 eV. • Photovoltaic performance of the in situ deposited nanocrystals is reported. • An improved PV performance compared to spin coated Schottky solar cells is shown.

  19. UO2 production process with methanol washing

    International Nuclear Information System (INIS)

    Sondermann, T.

    1978-01-01

    The invention refers to a process for the recovery of methanol used for washing the ammonium uranyl carbonate obtained during UO 2 production. The methanol contains about 50% H 2 O, about 10% (NH 4 ) 2 CO 3 , and is radioactive. According to the invention the methanol is purified at reduced pressure in a distillation unit and then led back to the washing unit. (UWI) 891 HP/UWI 892 MBE [de

  20. The fate of methanol in anaerobic bioreactors

    OpenAIRE

    Florencio, L.

    1994-01-01

    Methanol is an important component of certain industrial wastewaters. In anaerobic environments, methanol can be utilized by methanogens and acetogens. In wastewater treatment plants, the conversion of methanol into methane is preferred because this conversion is responsible for chemical oxygen demand (COD) removal, whereas with the formation of volatile fatty acids (VFA) little COD removal is achieved. Moreover, the accumulation of VFA can lead to reactor instability due to pH drops...

  1. Destruction of Energetic Materials in Supercritical Water

    Science.gov (United States)

    2002-06-25

    controls and difficulties associated with controlling processes and obtaining permits can negate potential advantages . Supercritical water oxidation...for H2 and an Alltech CTR-1 column with a temperature ramp program from -10 °C to 180 °C was used for the other gases. A mass spectrometer (HP 5971

  2. Electrodeposition of germanium from supercritical fluids.

    Science.gov (United States)

    Ke, Jie; Bartlett, Philip N; Cook, David; Easun, Timothy L; George, Michael W; Levason, William; Reid, Gillian; Smith, David; Su, Wenta; Zhang, Wenjian

    2012-01-28

    Several Ge(II) and Ge(IV) compounds were investigated as possible reagents for the electrodeposition of Ge from liquid CH(3)CN and CH(2)F(2) and supercritical CO(2) containing as a co-solvent CH(3)CN (scCO(2)) and supercritical CH(2)F(2) (scCH(2)F(2)). For Ge(II) reagents the most promising results were obtained using [NBu(n)(4)][GeCl(3)]. However the reproducibility was poor and the reduction currents were significantly less than the estimated mass transport limited values. Deposition of Ge containing films was possible at high cathodic potential from [NBu(n)(4)][GeCl(3)] in liquid CH(3)CN and supercritical CO(2) containing CH(3)CN but in all cases they were heavily contaminated by C, O, F and Cl. Much more promising results were obtained using GeCl(4) in liquid CH(2)F(2) and supercritical CH(2)F(2). In this case the reduction currents were consistent with mass transport limited reduction and bulk electrodeposition produced amorphous films of Ge. Characterisation by XPS showed the presence of low levels of O, F and C, XPS confirmed the presence of Ge together with germanium oxides, and Raman spectroscopy showed that the as deposited amorphous Ge could be crystallised by the laser used in obtaining the Raman measurements.

  3. Supercritical fluids technology. Pt. 1 General topics

    International Nuclear Information System (INIS)

    Marongiu, B.; De Giorgi, M. R.; Porcedda, S.; Cadoni, E.

    1998-01-01

    Supercritical fluids technology is among the emerging 'clean' technologies, that allows the minimization in the use of chemical and thermic treatments and products irradiation, diminishing the quantity of liquid wastes to be treated. In this first article phase equilibria thermodynamics and fluid mechanics of transport phenomena are reviewed [it

  4. Successful treatment with supercritical water oxidation

    International Nuclear Information System (INIS)

    Jensen, R.

    1994-01-01

    Supercritical Water Oxidation (SCWO) operates in a totally enclosed system. It uses water at high temperatures and high pressure to chemically change wastes. Oily substances become soluble and complex hydrocarbons are converted into water and carbon dioxide. Research and development on SCWO is described

  5. Chemical deposition methods using supercritical fluid solutions

    Science.gov (United States)

    Sievers, Robert E.; Hansen, Brian N.

    1990-01-01

    A method for depositing a film of a desired material on a substrate comprises dissolving at least one reagent in a supercritical fluid comprising at least one solvent. Either the reagent is capable of reacting with or is a precursor of a compound capable of reacting with the solvent to form the desired product, or at least one additional reagent is included in the supercritical solution and is capable of reacting with or is a precursor of a compound capable of reacting with the first reagent or with a compound derived from the first reagent to form the desired material. The supercritical solution is expanded to produce a vapor or aerosol and a chemical reaction is induced in the vapor or aerosol so that a film of the desired material resulting from the chemical reaction is deposited on the substrate surface. In an alternate embodiment, the supercritical solution containing at least one reagent is expanded to produce a vapor or aerosol which is then mixed with a gas containing at least one additional reagent. A chemical reaction is induced in the resulting mixture so that a film of the desired material is deposited.

  6. Catalytic depolymerization of lignin in supercritical ethanol

    NARCIS (Netherlands)

    Huang, X.; Koranyi, T.I.; Boot, M.D.; Hensen, E.J.M.

    2014-01-01

    One-step valorization of soda lignin in supercritical ethanol using a CuMgAlOx catalyst results in high monomer yield (23 wt¿%) without char formation. Aromatics are the main products. The catalyst combines excellent deoxygenation with low ring-hydrogenation activity. Almost half of the monomer

  7. Supercritical fluid carbon dioxide extraction of actinides

    International Nuclear Information System (INIS)

    Rao, Ankita; Tomar, B.S.

    2016-01-01

    Supercritical fluid extraction (SFE) is a process akin to liquid-liquid or solvent extraction where a Supercritical fluid (SCF) is contacted with a solid/ liquid matrix for the purpose of separating the component of interest from the original matrix. Carbon dioxide is a preferred choice as supercritical fluid (SCF) owing to its moderate critical parameter (P c = 7.38 MPa and T c = 304.1K) coupled with radiation and chemical stability, non toxic nature and low cost. Despite widespread applications for extraction of organic compounds and associated advantages especially liquid waste minimization, the SFE of metal ions was left unexplored for quite some time, as direct metal ion extraction is inefficient due charge neutralization requirement and weak solute-solvent interaction. Neutral SCF soluble metal-ligand complexation is imperative and SFE of actinides was reported only in 1994. Several studies have been carried out on SFE of uranium, thorium and plutonium from nitric acid medium employing different sets of ligands (organophosphorus, diketones, amides). Especially attractive is the possibility of direct dissolution and extraction of actinides employing ligand-acid adducts (like TBP.HNO 3 adduct) from solid matrices of different stages of nuclear fuel cycle viz. ores, spent nuclear fuels and radioactive wastes. Also, partitioning of actinides from fission products has been explored in spent nuclear fuel. These studies on supercritical fluid extraction of actinides indicate a more efficient and environmentally sustainable technology. (author)

  8. Structural behavior of supercritical fluids under confinement

    Science.gov (United States)

    Ghosh, Kanka; Krishnamurthy, C. V.

    2018-01-01

    The existence of the Frenkel line in the supercritical regime of a Lennard-Jones (LJ) fluid shown through molecular dynamics (MD) simulations initially and later corroborated by experiments on argon opens up possibilities of understanding the structure and dynamics of supercritical fluids in general and of the Frenkel line in particular. The location of the Frenkel line, which demarcates two distinct physical states, liquidlike and gaslike within the supercritical regime, has been established through MD simulations of the velocity autocorrelation (VACF) and radial distribution function (RDF). We, in this article, explore the changes in the structural features of supercritical LJ fluid under partial confinement using atomistic walls. The study is carried out across the Frenkel line through a series of MD simulations considering a set of thermodynamics states in the supercritical regime (P =5000 bar, 240 K ≤T ≤1500 K ) of argon well above the critical point. Confinement is partial, with atomistic walls located normal to z and extending to "infinity" along the x and y directions. In the "liquidlike" regime of the supercritical phase, particles are found to be distributed in distinct layers along the z axis with layer spacing less than one atomic diameter and the lateral RDF showing amorphous-like structure for specific spacings (packing frustration) and non-amorphous-like structure for other spacings. Increasing the rigidity of the atomistic walls is found to lead to stronger layering and increased structural order. For confinement with reflective walls, layers are found to form with one atomic diameter spacing and the lateral RDF showing close-packed structure for the smaller confinements. Translational order parameter and excess entropy assessment confirms the ordering taking place for atomistic wall and reflective wall confinements. In the "gaslike" regime of the supercritical phase, particle distribution along the spacing and the lateral RDF exhibit features

  9. Generation of gaseous methanol reference standards

    International Nuclear Information System (INIS)

    Geib, R.C.

    1991-01-01

    Methanol has been proposed as an automotive fuel component. Reliable, accurate methanol standards are essential to support widespread monitoring programs. The monitoring programs may include quantification of methanol from tailpipe emissions, evaporative emissions, plus ambient air methanol measurements. This paper will present approaches and results in the author's investigation to develop high accuracy methanol standards. The variables upon which the authors will report results are as follows: (1) stability of methanol gas standards, the studies will focus on preparation requirements and stability results from 10 to 1,000 ppmv; (2) cylinder to instrument delivery system components and purge technique, these studies have dealt with materials in contact with the sample stream plus static versus flow injection; (3) optimization of gas chromatographic analytical system will be discussed; (4) gas chromatography and process analyzer results and utility for methanol analysis will be presented; (5) the accuracy of the methanol standards will be qualified using data from multiple studies including: (a) gravimetric preparation; (b) linearity studies; (c) independent standards sources such as low pressure containers and diffusion tubes. The accuracy will be provided as a propagation of error from multiple sources. The methanol target concentrations will be 10 to 500 ppmv

  10. Methanol Extract of Myelophycus caespitosus Inhibits the ...

    African Journals Online (AJOL)

    Methanol Extract of Myelophycus caespitosus Inhibits the Inflammatory Response in Lipopolysaccharidestimulated BV2 Microglial Cells by Downregulating NF-kB via Inhibition of the Akt Signaling Pathway.

  11. Developments in the European methanol market

    International Nuclear Information System (INIS)

    Speed, J.

    1995-01-01

    In the late eighties/early nineties the World Methanol Market was basically divided into three regional markets--America, Asia Pacific and Europe. These markets were interrelated but each had its own specific characteristics and traditional suppliers. Now the situation has changed; in the mid nineties there is a Global Methanol Market with global players and effective global pricing and the European market is governed by events world-wide. Europe is however a specific market with specific characteristics which are different from those of other markets although it is also part of the Global Market. Hence before the author focuses on Europe he looks at the World Market. The paper discusses world methanol production and consumption by region, world methanol consumption by end use, world methanol supply demand balance, the west European market, western European methanol production, methanol imports to W. Europe, the Former Soviet Union supplies, W. European methanol consumption by end use, MTBE in Europe, duties on methanol imports into W. Europe, investment in Europe, the effect of the 1994/95 price spike, and key issues for the future of the industry

  12. Methanol in the L1551 Circumbinary Torus

    OpenAIRE

    White, Glenn J.; Fridlund, C. W. M.; Bergman, P.; Beardsmore, A.; Liseau, Rene; Phillips, R. R.

    2006-01-01

    We report observations of gaseous methanol in an edge-on torus surrounding the young stellar object L1551 IRS5. The peaks in the torus are separated by ~ 10,000 AU from L1551 IRS5, and contain ~ 0.03 earth masses of cold methanol. We infer that the methanol abundance increases in the outer part of the torus, probably as a result of methanol evaporation from dust grain surfaces heated by the shock luminosity associated with the shocks associated with the jets of an externally located x-ray sou...

  13. Soil and groundwater remediation guidelines for methanol

    International Nuclear Information System (INIS)

    2010-12-01

    Methanol is used by oil and gas operators to inhibit hydrate formation in the recovery of heavy oils, in natural gas production and transport, as well as in various other production applications. Emissions from methanol primary occur from miscellaneous solvent usage, methanol production, end-product manufacturing, and storage and handling losses. This document provided soil and groundwater remediation guidelines for methanol releases into the environment. The guidelines were consistent with the Alberta Environment tier 1 soil and groundwater framework. The chemical and physical properties of methanol were reviewed. The environmental fate and behavior of methanol releases was discussed, and the behaviour and effects of methanol in terrestrial and aquatic biota were evaluated. The toxicity of methanol and its effects in humans and mammalian species were reviewed. Soil quality and ground water quality guidelines were presented. Surface water and soil guideline calculation methods were provided, and ecological exposure and ground water pathways were discussed. Management limits for methanol concentrations were also provided. 162 refs., 18 tabs., 4 figs.

  14. Determination of methanol in Iranian herbal distillates.

    Science.gov (United States)

    Shirani, Kobra; Hassani, Faezeh Vahdati; Azar-Khiavi, Kamal Razavi; Moghaddam, Zohreh Samie; Karimi, Gholamreza

    2016-06-01

    Herbal distillates have been used as beverages, for flavoring, or as phytomedicines in many countries for a long time. Recently, the occurrence of blindness after drinking herbal distillates has created concerns in Iran. The aim of this study was to determine the concentrations of methanol in herbal distillates produced in Iran. Eighty-four most commonly used herbal distillates purchased from herbal distillate factories were analyzed for methanol contents by gas chromatography and flame ionization detection, with ethanol as internal standard. In 15 herbal distillates, the methanol concentration was below the limit of quantitation. The methanol concentrations in all samples ranged from 43 to 277 mg/L. Forty-five samples contained methanol in excess of the Iranian standard. The maximum concentration was found in an herbal distillate of Mentha piperita (factory E) (277±12), and the minimum in a distillate of Carum carvi (factory B) (42.6 ± 0.5). Since the 45 Iranian herbal distillates containing methanol levels were beyond the legal limits according to the Iranian standard, it seems necessary to monitor the amount of methanol and give a warning to watch out for the latent risk problem of methanol uptake, and establish a definitive relationship between the degree of intoxication observed and the accumulation of methanol in the blood.

  15. Simultaneous analysis for water- and fat-soluble vitamins by a novel single chromatography technique unifying supercritical fluid chromatography and liquid chromatography.

    Science.gov (United States)

    Taguchi, Kaori; Fukusaki, Eiichiro; Bamba, Takeshi

    2014-10-03

    Chromatography techniques usually use a single state in the mobile phase, such as liquid, gas, or supercritical fluid. Chromatographers manage one of these techniques for their purpose but are sometimes required to use multiple methods, or even worse, multiple techniques when the target compounds have a wide range of chemical properties. To overcome this challenge, we developed a single method covering a diverse compound range by means of a "unified" chromatography which completely bridges supercritical fluid chromatography and liquid chromatography. In our method, the phase state was continuously changed in the following order; supercritical, subcritical and liquid. Moreover, the gradient of the mobile phase starting at almost 100% CO2 was replaced with 100% methanol at the end completely. As a result, this approach achieved further extension of the polarity range of the mobile phase in a single run, and successfully enabled the simultaneous analysis of fat- and water-soluble vitamins with a wide logP range of -2.11 to 10.12. Furthermore, the 17 vitamins were exceptionally separated in 4min. Our results indicated that the use of dense CO2 and the replacement of CO2 by methanol are practical approaches in unified chromatography covering diverse compounds. Additionally, this is a first report to apply the novel approach to unified chromatography, and can open another door for diverse compound analysis in a single chromatographic technique with single injection, single column and single system. Copyright © 2014. Published by Elsevier B.V.

  16. Improvement of biodiesel methanol blends

    Directory of Open Access Journals (Sweden)

    Y. Datta Bharadwaz

    2016-06-01

    Full Text Available The main objective of this work was to improve the performance of biodiesel–methanol blends in a VCR engine by using optimized engine parameters. For optimization of the engine, operational parameters such as compression ratio, fuel blend, and load are taken as factors, whereas performance parameters such as brake thermal efficiency (Bth and brake specific fuel consumption (Bsfc and emission parameters such as carbon monoxide (CO, unburnt hydrocarbons (HC, Nitric oxides (NOx and smoke are taken as responses. Experimentation is carried out as per the design of experiments of the response surface methodology. Optimization of engine operational parameters is carried out using Derringers Desirability approach. From the results obtained it is inferred that the VCR engine has maximum performance and minimum emissions at 18 compression ratio, 5% fuel blend and at 9.03 kg of load. At this optimized operating conditions of the engine the responses such as brake thermal efficiency, brake specific fuel consumption, carbon monoxide, unburnt hydrocarbons, nitric oxide, and smoke are found to be 31.95%, 0.37 kg/kW h, 0.036%, 5 ppm, 531.23 ppm and 15.35% respectively. It is finally observed from the mathematical models and experimental data that biodiesel methanol blends have maximum efficiency and minimum emissions at optimized engine parameters.

  17. Supercritical water oxidation benchscale testing metallurgical analysis report

    International Nuclear Information System (INIS)

    Norby, B.C.

    1993-02-01

    This report describes metallurgical evaluation of witness wires from a series of tests using supercritical water oxidation (SCWO) to process cutting oil containing a simulated radionuclide. The goal of the tests was to evaluate the technology's ability to process a highly chlorinated waste representative of many mixed waste streams generated in the DOE complex. The testing was conducted with a bench-scale SCWO system developed by the Modell Development Corporation. Significant test objectives included process optimization for adequate destruction efficiency, tracking the radionuclide simulant and certain metals in the effluent streams, and assessment of reactor material degradation resulting from processing a highly chlorinated waste. The metallurgical evaluation described herein includes results of metallographic analysis and Scanning Electron Microscopy analysis of witness wires exposed to the SCWO environment for one test series

  18. Supercritical fluid chromatography coupled with in-source atmospheric pressure ionization hydrogen/deuterium exchange mass spectrometry for compound speciation.

    Science.gov (United States)

    Cho, Yunju; Choi, Man-Ho; Kim, Byungjoo; Kim, Sunghwan

    2016-04-29

    An experimental setup for the speciation of compounds by hydrogen/deuterium exchange (HDX) with atmospheric pressure ionization while performing chromatographic separation is presented. The proposed experimental setup combines the high performance supercritical fluid chromatography (SFC) system that can be readily used as an inlet for mass spectrometry (MS) and atmospheric pressure photo ionization (APPI) or atmospheric pressure chemical ionization (APCI) HDX. This combination overcomes the limitation of an approach using conventional liquid chromatography (LC) by minimizing the amount of deuterium solvents used for separation. In the SFC separation, supercritical CO2 was used as a major component of the mobile phase, and methanol was used as a minor co-solvent. By using deuterated methanol (CH3OD), AP HDX was achieved during SFC separation. To prove the concept, thirty one nitrogen- and/or oxygen-containing standard compounds were analyzed by SFC-AP HDX MS. The compounds were successfully speciated from the obtained SFC-MS spectra. The exchange ions were observed with as low as 1% of CH3OD in the mobile phase, and separation could be performed within approximately 20min using approximately 0.24 mL of CH3OD. The results showed that SFC separation and APPI/APCI HDX could be successfully performed using the suggested method. Copyright © 2016 Elsevier B.V. All rights reserved.

  19. Systematic investigations of peak deformations due to co-solvent adsorption in preparative supercritical fluid chromatography.

    Science.gov (United States)

    Glenne, Emelie; Leek, Hanna; Klarqvist, Magnus; Samuelsson, Jörgen; Fornstedt, Torgny

    2017-05-05

    Strangely shaped overloaded bands were recently reported using a standard supercritical fluid chromatographic system comprising a diol column as the stationary phase and carbon dioxide with methanol as the mobile phase. Some of these overloaded elution profiles appeared strongly deformed and even had "anti-Langmuirian" shapes although their solute compounds had "Langmuirian" adsorption. To obtain a more complete understanding of the generality of these effects, the investigation was expanded to cover also other common co-solvents, such as ethanol, 2-propanol, and acetonitrile, as well as various stationary phase materials, such as silica, and 2-ethylpyridine. From this expanded study it could be confirmed that the effects of deformed overloaded solute band shapes, due to co-solvent adsorption, is general phenomena in supercritical fluid chromatographic. It could also be concluded that these effects as well as previously observed "solvent effects" or "plug effects" are entirely due to competition between the solute and solvent molecules for the adsorption sites on the stationary phase surface. Finally, guidelines were given for how to evaluate the risk of deformations occurring for a given solvent-column combination, based simply on testing retention times of solutes and co-solvent. Copyright © 2017 Elsevier B.V. All rights reserved.

  20. Preparation of 5-fluorouracil nanoparticles by supercritical antisolvents for pulmonary delivery

    Directory of Open Access Journals (Sweden)

    Pardis Kalantarian

    2010-09-01

    Full Text Available Pardis Kalantarian1,2, Abdolhosein Rouholamini Najafabadi1, Ismaeil Haririan2, Alireza Vatanara1, Yadollah Yamini3, Majid Darabi1, Kambiz Gilani11Aerosol Research Laboratory and 2Pharmaceutical Laboratory, School of Pharmacy, Tehran University of Medical Sciences, 3Department of Chemistry, Tarbiat Modarres University, Tehran, IranAbstract: This study concerns the supercritical antisolvent process which allows single-step production of 5-fluorouracil (5-FU nanoparticles. This process enhances the physical characteristics of 5-FU in order to deliver it directly to the respiratory tract. Several mixtures of methanol with dichloromethane, acetone, or ethanol were used for particle preparation, and their effects on the physical characteristics of the final products were studied. The conditions of the experiment included pressures of 100 and 150 bar, temperature of 40°C, and a flow rate of 1 mL/min. The particles were characterized physicochemically before and after the process for their morphology and crystallinity. In spite of differences in size, the particles were not very different regarding their morphology. The resulting particles were of a regular shape, partly spherical, and appeared to have a smooth surface, whereas the mechanically milled particles showed less uniformity, had surface irregularities and a high particle size distribution, and seemed aggregated. Particles of 5-FU precipitated from methanol-dichloromethane 50:50 had a mean particle size of 248 nm. In order to evaluate the aerodynamic behavior of the nanoparticles, six 5-FU dry powder formulations containing mixtures of coarse and fine lactose of different percentages were prepared. Deposition of 5-FU was measured using a twin-stage liquid impinger and analyzed using a validated high pressure liquid chromatography method. Addition of fine lactose improved the aerodynamic performance of the drug, as determined by the fine particle fraction.Keywords: supercritical antisolvent, 5

  1. Comparison of ultra high performance supercritical fluid chromatography, ultra high performance liquid chromatography, and gas chromatography for the separation of synthetic cathinones.

    Science.gov (United States)

    Carnes, Stephanie; O'Brien, Stacey; Szewczak, Angelica; Tremeau-Cayel, Lauriane; Rowe, Walter F; McCord, Bruce; Lurie, Ira S

    2017-09-01

    A comparison of ultra high performance supercritical fluid chromatography, ultra high performance liquid chromatography, and gas chromatography for the separation of synthetic cathinones has been conducted. Nine different mixtures of bath salts were analyzed in this study. The three different chromatographic techniques were examined using a general set of controlled synthetic cathinones as well as a variety of other synthetic cathinones that exist as positional isomers. Overall 35 different synthetic cathinones were analyzed. A variety of column types and chromatographic modes were examined for developing each separation. For the ultra high performance supercritical fluid chromatography separations, analyses were performed using a series of Torus and Trefoil columns with either ammonium formate or ammonium hydroxide as additives, and methanol, ethanol or isopropanol organic solvents as modifiers. Ultra high performance liquid chromatographic separations were performed in both reversed phase and hydrophilic interaction chromatographic modes using SPP C18 and SPP HILIC columns. Gas chromatography separations were performed using an Elite-5MS capillary column. The orthogonality of ultra high performance supercritical fluid chromatography, ultra high performance liquid chromatography, and gas chromatography was examined using principal component analysis. For the best overall separation of synthetic cathinones, the use of ultra high performance supercritical fluid chromatography in combination with gas chromatography is recommended. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. High-Performance Direct Methanol Fuel Cells with Precious-Metal-Free Cathode.

    Science.gov (United States)

    Li, Qing; Wang, Tanyuan; Havas, Dana; Zhang, Hanguang; Xu, Ping; Han, Jiantao; Cho, Jaephil; Wu, Gang

    2016-11-01

    Direct methanol fuel cells (DMFCs) hold great promise for applications ranging from portable power for electronics to transportation. However, apart from the high costs, current Pt-based cathodes in DMFCs suffer significantly from performance loss due to severe methanol crossover from anode to cathode. The migrated methanol in cathodes tends to contaminate Pt active sites through yielding a mixed potential region resulting from oxygen reduction reaction and methanol oxidation reaction. Therefore, highly methanol-tolerant cathodes must be developed before DMFC technologies become viable. The newly developed reduced graphene oxide (rGO)-based Fe-N-C cathode exhibits high methanol tolerance and exceeds the performance of current Pt cathodes, as evidenced by both rotating disk electrode and DMFC tests. While the morphology of 2D rGO is largely preserved, the resulting Fe-N-rGO catalyst provides a more unique porous structure. DMFC tests with various methanol concentrations are systematically studied using the best performing Fe-N-rGO catalyst. At feed concentrations greater than 2.0 m, the obtained DMFC performance from the Fe-N-rGO cathode is found to start exceeding that of a Pt/C cathode. This work will open a new avenue to use nonprecious metal cathode for advanced DMFC technologies with increased performance and at significantly reduced cost.

  3. Review on utilization of the pervaporation membrane for passive vapor feed direct methanol fuel cell

    International Nuclear Information System (INIS)

    Fauzi, N F I; Hasran, U A; Kamarudin, S K

    2013-01-01

    The Direct Methanol Fuel Cell (DMFC) is a promising portable power source for mobile electronic devices because of its advantages including easy fuel storage, high energy density, low temperature operation and compact structure. In DMFC, methanol is used as a fuel source where it can be fed in liquid or vapor phase. However, the vapor feed DMFC has an advantage over the liquid feed system as it has the potential to have a higher operating temperature to increase the reaction rates and power outputs, to enhance the mass transfers, to reduce methanol crossover, reliable for high methanol concentration and it can increase the fuel cell performance. Methanol vapor can be delivered to the anode by using a pervaporation membrane, heating the liquid methanol or another method that compatible. Therefore, this paper is a review on vapor feed DMFC as a better energy source than liquid feed DMFC, the pervaporation membrane used to vaporize methanol feed from the reservoir and its applications in vapor feed DMFC

  4. Modelling the competition between sulphate reducers and methanogens in a thermophilic methanol-fed bioreactor

    NARCIS (Netherlands)

    Spanjers, H.; Weijma, J.; Abusam, A.

    2002-01-01

    Sulphate can be removed from wastewater by means of biological anaerobic reduction to sulphide. The reduction requires the presence of a substrate that can serve as an electron donor. Methanol a suitable electron donor for sulphate reduction under thermophilic conditions. In an anaerobic system

  5. Electro-oxidation of methanol on copper in alkaline solution

    International Nuclear Information System (INIS)

    Heli, H.; Jafarian, M.; Mahjani, M.G.; Gobal, F.

    2004-01-01

    The electro-oxidation of methanol on copper in alkaline solutions has been studied by the methods of cyclic voltammetry, quasi-steady state polarization and chronoamperometry. It has been found that in the course of an anodic potential sweep the electro-oxidation of methanol follows the formation of Cu III and is catalysed by this species through a mediated electron transfer mechanism. The reaction also continues in the early stages of the reversed cycle until it is stopped by the prohibitively negative potentials. The process is diffusion controlled and the current-time responses follow Cottrellian behavior. The rate constants, turnover frequency, anodic transfer coefficient and the apparent activation energy of the electro-oxidation reaction are reported

  6. Solar photocatalytic conversion of CO{sub 2} to methanol

    Energy Technology Data Exchange (ETDEWEB)

    Ryba, G.; Shelnutt, J.; Prairie, M.R.; Assink, R.A.

    1997-02-01

    This report summarizes the three-year LDRD program directed at developing catalysts based on metalloporphyrins to reduce carbon dioxide. Ultimately it was envisioned that such catalysts could be made part of a solar-driven photoredox cycle by coupling metalloporphyrins with semiconductor systems. Such a system would provide the energy required for CO{sub 2} reduction to methanol, which is an uphill 6-electron reduction. Molecular modeling and design capabilities were used to engineer metalloporphyrin catalysts for converting CO{sub 2} to CO and higher carbon reduction products like formaldehyde, formate, and methanol. Gas-diffusion electrochemical cells were developed to carry out these reactions. A tin-porphyrin/alumina photocatalyst system was partially developed to couple solar energy to this reduction process.

  7. Methanol conversion to lower olefins over RHO type zeolite

    KAUST Repository

    Masih, Dilshad

    2013-07-01

    Eight-membered ring small-pore zeolite of RHO-type topology has been synthesized, characterized and tested for methanol-to-olefin (MTO) reaction. The zeolite was hydrothermally crystallized from the gel with Si/Al ratio of 5.0. It showed a high BET specific surface area (812 m2 g-1), micropore volume (0.429 cm3 g-1), and acid amount (2.53 mmol g-1). Scanning electron microscopy observations showed small crystallites of about 1 μm. The zeolite was active for MTO reaction with 100% methanol conversions at 623-723 K, whereas selectivity to lower olefins changed with time. © 2013 Elsevier B.V.

  8. Supercritical Fluids Processing of Biomass to Chemicals and Fuels

    Energy Technology Data Exchange (ETDEWEB)

    Olson, Norman K. [Iowa State Univ., Ames, IA (United States)

    2011-09-28

    The main objective of this project is to develop and/or enhance cost-effective methodologies for converting biomass into a wide variety of chemicals, fuels, and products using supercritical fluids. Supercritical fluids will be used both to perform reactions of biomass to chemicals and products as well as to perform extractions/separations of bio-based chemicals from non-homogeneous mixtures. This work supports the Biomass Program’s Thermochemical Platform Goals. Supercritical fluids are a thermochemical approach to processing biomass that, while aligned with the Biomass Program’s interests in gasification and pyrolysis, offer the potential for more precise and controllable reactions. Indeed, the literature with respect to the use of water as a supercritical fluid frequently refers to “supercritical water gasification” or “supercritical water pyrolysis.”

  9. Bio-oil production from biomass via supercritical fluid extraction

    Energy Technology Data Exchange (ETDEWEB)

    Durak, Halil, E-mail: halildurak@yyu.edu.tr [Yuzuncu Yıl University, Vocational School of Health Services, 65080, Van (Turkey)

    2016-04-18

    Supercritical fluid extraction is used for producing bio-fuel from biomass. Supercritical fluid extraction process under supercritical conditions is the thermally disruption process of the lignocellulose or other organic materials at 250-400 °C temperature range under high pressure (4-5 MPa). Supercritical fluid extraction trials were performed in a cylindrical reactor (75 mL) in organic solvents (acetone, ethanol) under supercritical conditions with (calcium hydroxide, sodium carbonate) and without catalyst at the temperatures of 250, 275 and 300 °C. The produced liquids at 300 °C in supercritical liquefaction were analyzed and characterized by elemental, GC-MS and FT-IR. 36 and 37 different types of compounds were identified by GC-MS obtained in acetone and ethanol respectively.

  10. Supercritical fluid technologies for ceramic-processing applications

    International Nuclear Information System (INIS)

    Matson, D.W.; Smith, R.D.

    1989-01-01

    This paper reports on the applications of supercritical fluid technologies for ceramic processing. The physical and chemical properties of these densified gases are summarized and related to their use as solvents and processing media. Several areas are identified in which specific ceramic processes benefit from the unique properties of supercritical fluids. The rapid expansion of supercritical fluid solutions provides a technique for producing fine uniform powders and thin films of widely varying materials. Supercritical drying technologies allow the formation of highly porous aerogel products with potentially wide application. Hydrothermal processes leading to the formation of large single crystals and microcrystalline powders can also be extended into the supercritical regime of water. Additional applications and potential applications are identified in the areas of extraction of binders and other additives from ceramic compacts, densification of porous ceramics, the formation of powders in supercritical micro-emulsions, and in preceramic polymer processing

  11. Bio-oil production from biomass via supercritical fluid extraction

    International Nuclear Information System (INIS)

    Durak, Halil

    2016-01-01

    Supercritical fluid extraction is used for producing bio-fuel from biomass. Supercritical fluid extraction process under supercritical conditions is the thermally disruption process of the lignocellulose or other organic materials at 250-400 °C temperature range under high pressure (4-5 MPa). Supercritical fluid extraction trials were performed in a cylindrical reactor (75 mL) in organic solvents (acetone, ethanol) under supercritical conditions with (calcium hydroxide, sodium carbonate) and without catalyst at the temperatures of 250, 275 and 300 °C. The produced liquids at 300 °C in supercritical liquefaction were analyzed and characterized by elemental, GC-MS and FT-IR. 36 and 37 different types of compounds were identified by GC-MS obtained in acetone and ethanol respectively.

  12. ( Asteraceae ) methanol extracts against Helicobacter pylori

    African Journals Online (AJOL)

    Methanol vehicle did not affect H. pylori growth. Conclusion: The observed antibacterial effect of G. glutinosum extracts may be of benefit as an adjuvant treatment of diseases caused by H. pylori. Key words: Gymnosperma glutinosum, Helicobacter pylori, methanol extract, minimal inhibitory concentration (MIC).

  13. Developmental and Reproductive Toxicology of Methanol

    Science.gov (United States)

    Methanol is a high production volume chemical used as a feedstock for chemical syntheses and as a solvent and fuel additive. Methanol is acutely toxic to humans, causing acidosis, blindness in death at high dosages, but its developmental and reproductive toxicity in humans is poo...

  14. Methanol as fuel: evaluation of atmosphere contamination

    International Nuclear Information System (INIS)

    Alonso, C.D.; Romano, J.; Guardani, M.L.G.

    1991-01-01

    With the beginning of methanol use as automotive fuel in Sao Paulo city, 1990, were realized special measurements of methanol, formaldehyde, ethanol and acetaldehyde in atmosphere. Other indicators of air quality as carbon and ozone monoxide were also observed in this study. (C.M.)

  15. Separation of furostanol saponins by supercritical fluid chromatography.

    Science.gov (United States)

    Yang, Jie; Zhu, Lingling; Zhao, Yang; Xu, Yongwei; Sun, Qinglong; Liu, Shuchen; Liu, Chao; Ma, Baiping

    2017-10-25

    Supercritical fluid chromatography (SFC) has good separation efficiency and is suitable for separating weakly polar compounds. Furostanol saponins, as an important kind of steroidal saponins, generally have two sugar chains, which are polar and hydrophilic. The hydroxyl group at the C-22 position of furostanol saponins is active and easily reacts with lower alcohols under appropriate conditions. The separation of hydrophilic furostanol saponins was tested by SFC in this study. The effects of chromatographic conditions on the separation of the mixed furostanol saponins and their hydroxyl derivatives at the C-22 position were studied. The conditions for SFC, which included different column polarity, modifier, additive, and column temperature, were tested. After optimization, the mixed 10 similar structures of furostanol saponins were separated in 22min on the Diol column at a temperature of 40°C. The mobile phase was CO 2 (mobile phase A) and methanol (containing 0.2% NH 3 ∙H 2 O and 3% H 2 O) (mobile phase B). The backpressure was maintained isobarically at 11.03MPa. SFC was found to be effective in separating the furostanol saponins that shared the same aglycone but varied in sugar chains. SFC was sensitive to the number and type of sugars. The resolution of furostanol saponin isomers was not ideal. The extract of Dioscorea zingiberensis C. H. Wright was profiled by SFC-quadrupole time-of-flight mass spectrometry. The main saponins of the extract were well separated. Therefore, SFC could be used for separating hydrophilic furostanol saponins and analyzing traditional Chinese medicines that mainly contained steroidal saponins. Copyright © 2017 Elsevier B.V. All rights reserved.

  16. Industrial applications and current trends in supercritical fluid technologies

    OpenAIRE

    Gamse Thomas

    2005-01-01

    Supercritical fluids have a great potential for wide fields of processes Although CO2 is still one of the most used supercritical gases, for special purposes propane or even fluorinated-chlorinated fluids have also been tested. The specific characteristics of supercritical fluids behaviour were analyzed such as for example the solubilities of different components and the phase equilibria between the solute and solvent. The application at industrial scale (decaffeinating of tea and coffee, hop...

  17. Production of methanol/DME from biomass

    DEFF Research Database (Denmark)

    Ahrenfeldt, Jesper; Henriksen, Ulrik Birk; Münster-Swendsen, Janus

    In this project the production of DME/methanol from biomass has been investigated. Production of DME/methanol from biomass requires the use of a gasifier to transform the solid fuel to a synthesis gas (syngas) - this syngas can then be catalytically converted to DME/methanol. Two different gasifier...... cleaning. This was proved by experiments. Thermodynamic computer models of DME and methanol plants based on using the Two-Stage Gasification concept were created to show the potential of such plants. The models showed that the potential biomass to DME/methanol + net electricity energy efficiency was 51...... gasification, but little information exists on using these types of gasifiers for biomass gasification. The experiments performed provided quantitative data on product and gas composition as a function of operation conditions. Biomass can be gasified with less oxygen consumption compared to coal. The organic...

  18. Investigations into low pressure methanol synthesis

    DEFF Research Database (Denmark)

    Sharafutdinov, Irek

    The central topic of this work has been synthesis, characterization and optimization of novel Ni-Ga based catalysts for hydrogenation of CO2 to methanol. The overall goal was to search for materials that could be used as a low temperature (and low pressure) methanol synthesis catalyst....... This is required for small scale delocalized methanol production sites, where installation of energy demanding compression units should be avoided. The work was triggered by DFT calculations, which showed that certain bimetallic systems are active towards methanol synthesis from CO2 and H2 at ambient pressure...... containing 5:3 molar ratio of Ni:Ga, the intrinsic activity (methanol production rate per active surface area) is comparable to that of highly optimised Cu/ZnO/Al2O3. Formation of the catalyst was investigated with the aid of in-situ XRD and in-situ XAS techniques. The mechanism of alloying was proposed...

  19. Recycling of greenhouse gases via methanol

    Energy Technology Data Exchange (ETDEWEB)

    Bill, A [Paul Scherrer Inst. (PSI), Villigen (Switzerland); Eliasson, B; Kogelschatz, U [ABB Corporate Research Center, Baden-Daettwil (Switzerland)

    1997-06-01

    Greenhouse gas emissions to the atmosphere can be mitigated by using direct control technologies (capture, disposal or chemical recycling). We report on carbon dioxide and methane recycling with other chemicals, especially with hydrogen and oxygen, to methanol. Methanol synthesis from CO{sub 2} is investigated on various catalysts at moderate pressures ({<=}30 bar) and temperatures ({<=}300{sup o}C). The catalysts show good methanol activities and selectivities. The conversion of CO{sub 2} and CH{sub 4} to methanol is also studied in a silent electrical discharge at pressures of 1 to 4 bar and temperatures close to room temperature. Methanol yields are given for mixtures of CO{sub 2}/H{sub 2}, CH{sub 4}/O{sub 2} and also for CH{sub 4} and air mixtures. (author) 2 figs., 5 refs.

  20. Supercritical CO{sub 2} mediated synthesis and catalytic activity of graphene/Pd nanocomposites

    Energy Technology Data Exchange (ETDEWEB)

    Tang, Lulu [School of Chemical Engineering, Yeungnam University, Gyeongsan, Gyeoungbuk 712-749 (Korea, Republic of); Nguyen, Van Hoa [School of Chemical Engineering, Yeungnam University, Gyeongsan, Gyeoungbuk 712-749 (Korea, Republic of); Department of Chemistry, Nha Trang University, 2 Nguyen Dinh Chieu, Nha Trang (Viet Nam); Shim, Jae-Jin, E-mail: jjshim@yu.ac.kr [School of Chemical Engineering, Yeungnam University, Gyeongsan, Gyeoungbuk 712-749 (Korea, Republic of)

    2015-11-15

    Highlights: • RGO/Pd composite was efficiently prepared via a facile method in supercritical CO{sub 2}. • Graphene sheets were coated uniformly with Pd nanoparticles with a size of ∼8 nm. • Composites exhibited excellent catalytic activity in the Suzuki reaction even after 10 cycles. - Abstract: Graphene sheets were decorated with palladium nanoparticles using a facile and efficient method in supercritical CO{sub 2}. The nanoparticles were formed on the graphene sheets by the simple hydrogen reduction of palladium(II) hexafluoroacetylacetonate precursor in supercritical CO{sub 2}. The product was characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, and X-ray photoelectron spectroscopy. Highly dispersed nanoparticles with various sizes and shapes adhered well to the graphene sheets. The composites showed high catalytic activities for the Suzuki reaction under aqueous and aerobic conditions within 5 min. The effects of the different Pd precursor loadings on the catalytic activities of the composites were also examined.

  1. Preliminary Hazard Analysis of Supercritical Fluid Separation of Energetic Materials

    National Research Council Canada - National Science Library

    1997-01-01

    .... Army Research Laboratory (ARL) and elsewhere, particularly at the Phasex Corporation, Lawrence, MA, has demonstrated the feasibility of separating the energetic moieties by use of supercritical CO2...

  2. Supercritical boiler material selection using fuzzy analytic network process

    Directory of Open Access Journals (Sweden)

    Saikat Ranjan Maity

    2012-08-01

    Full Text Available The recent development of world is being adversely affected by the scarcity of power and energy. To survive in the next generation, it is thus necessary to explore the non-conventional energy sources and efficiently consume the available sources. For efficient exploitation of the existing energy sources, a great scope lies in the use of Rankin cycle-based thermal power plants. Today, the gross efficiency of Rankin cycle-based thermal power plants is less than 28% which has been increased up to 40% with reheating and regenerative cycles. But, it can be further improved up to 47% by using supercritical power plant technology. Supercritical power plants use supercritical boilers which are able to withstand a very high temperature (650-720˚C and pressure (22.1 MPa while producing superheated steam. The thermal efficiency of a supercritical boiler greatly depends on the material of its different components. The supercritical boiler material should possess high creep rupture strength, high thermal conductivity, low thermal expansion, high specific heat and very high temperature withstandability. This paper considers a list of seven supercritical boiler materials whose performance is evaluated based on seven pivotal criteria. Given the intricacy and difficulty of this supercritical boiler material selection problem having interactions and interdependencies between different criteria, this paper applies fuzzy analytic network process to select the most appropriate material for a supercritical boiler. Rene 41 is the best supercritical boiler material, whereas, Haynes 230 is the worst preferred choice.

  3. Kinetics of Chemical Agents Destruction in Supercritical Water

    National Research Council Canada - National Science Library

    Tester, Jefferson

    2003-01-01

    .... An experimental study of methylphosphonic acid (MPA) oxidation has been completed that includes macroscopic modeling of the overall global rate law for MPA oxidation in supercritical water (SCW...

  4. Evaluation of supercritical CO2 dried cellulose aerogels as nano-biomaterials

    Science.gov (United States)

    Lee, Sinah; Kang, Kyu-Young; Jeong, Myung-Joon; Potthast, Antje; Liebner, Falk

    2017-10-01

    Cellulose is the renewable, biodegradable and abundant resource and is suggested as an alternative material to silica due to the high price and environmental load of silica. The first step for cellulose aerogel production is to dissolve cellulose, and hydrated calcium thiocyanate molten salt is one of the most effective solvents for preparing porous material. Cellulose aerogels were prepared from dissolved cellulose samples of different degree of polymerization (DP) and drying methods, and tested with shrinkage, density and mechanical strength. Supercritical CO2 dried cellulose aerogels shrank less compared to freeze-dried cellulose aerogels, whereas the densities were increased according to the DP increases in both cellulose aerogels. Furthermore, scanning electron microscope (SEM) images showed that the higher DP cellulose aerogels were more uniform with micro-porous structure. Regarding the mechanical strength of cellulose aerogels, supercritical CO2 dried cellulose aerogels with higher molecular weight were much more solid.

  5. One-pot synthesis of graphene supported platinum–cobalt nanoparticles as electrocatalysts for methanol oxidation

    International Nuclear Information System (INIS)

    Kepenienė, V.; Tamašauskaitė-Tamašiūnaitė, L.; Jablonskienė, J.; Semaško, M.; Vaičiūnienė, J.; Vaitkus, R.; Norkus, E.

    2016-01-01

    In the present study the graphene supported platinum–cobalt nanoparticles were prepared via microwave synthesis. The composition of prepared catalysts was examined by Inductively Coupled Plasma Optical Emission Spectroscopy. The shape and size of catalyst particles were determined by Transmission Electron Microscopy. The electrocatalytic activity of the graphene supported platinum–cobalt nanoparticles was investigated towards the electro-oxidation of methanol in an alkaline medium. It has been found that the graphene supported platinum–cobalt nanoparticles having the Pt:Co molar ratio 1:7 show the highest activity towards the electro-oxidation of methanol among the catalysts with the Pt:Co molar ratios equal to 1:1 and 1:44, graphene supported bare Co and Pt/C catalysts. - Highlights: • Preparation of graphene supported Pt-Co nanoparticles by microwave synthesis. • Electrocatalysts for oxidation of methanol. • Higher activity of PtCo/graphene towards methanol oxidation.

  6. Selective electrocatalysts toward a prototype of the membraneless direct methanol fuel cell.

    Science.gov (United States)

    Feng, Yan; Yang, Jinhua; Liu, Hui; Ye, Feng; Yang, Jun

    2014-01-22

    Mastery over the structure of nanomaterials enables control of their properties to enhance their performance for a given application. Herein we demonstrate the design and fabrication of Pt-based nanomaterials with enhanced catalytic activity and superior selectivity toward the reactions in direct methanol fuel cells (DMFCs) upon the deep understanding of the mechanisms of these electrochemical reactions. In particular, the ternary Au@Ag2S-Pt nanocomposites display superior methanol oxidation reaction (MOR) selectivity due to the electronic coupling effect among different domains of the nanocomposites, while the cage-bell structured Pt-Ru nanoparticles exhibit excellent methanol tolerance for oxygen reduction reaction (ORR) at the cathode because of the differential diffusion of methanol and oxygen in the porous Ru shell of the cage-bell nanoparticles. The good catalytic selectivity of these Pt-based nanomaterials via structural construction enables a DMFC to be built without a proton exchange membrane between the fuel electrode and the oxygen electrode.

  7. One-pot synthesis of graphene supported platinum–cobalt nanoparticles as electrocatalysts for methanol oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Kepenienė, V., E-mail: virginalisk@gmail.com [Department of Catalysis, Center for Physical Sciences and Technology, Vilnius LT 01108 (Lithuania); Tamašauskaitė-Tamašiūnaitė, L.; Jablonskienė, J.; Semaško, M.; Vaičiūnienė, J. [Department of Catalysis, Center for Physical Sciences and Technology, Vilnius LT 01108 (Lithuania); Vaitkus, R. [Faculty of Chemistry, Vilnius University, Vilnius LT 03225 (Lithuania); Norkus, E. [Department of Catalysis, Center for Physical Sciences and Technology, Vilnius LT 01108 (Lithuania)

    2016-03-01

    In the present study the graphene supported platinum–cobalt nanoparticles were prepared via microwave synthesis. The composition of prepared catalysts was examined by Inductively Coupled Plasma Optical Emission Spectroscopy. The shape and size of catalyst particles were determined by Transmission Electron Microscopy. The electrocatalytic activity of the graphene supported platinum–cobalt nanoparticles was investigated towards the electro-oxidation of methanol in an alkaline medium. It has been found that the graphene supported platinum–cobalt nanoparticles having the Pt:Co molar ratio 1:7 show the highest activity towards the electro-oxidation of methanol among the catalysts with the Pt:Co molar ratios equal to 1:1 and 1:44, graphene supported bare Co and Pt/C catalysts. - Highlights: • Preparation of graphene supported Pt-Co nanoparticles by microwave synthesis. • Electrocatalysts for oxidation of methanol. • Higher activity of PtCo/graphene towards methanol oxidation.

  8. Etching of glass microchips with supercritical water

    Czech Academy of Sciences Publication Activity Database

    Karásek, Pavel; Grym, Jakub; Roth, Michal; Planeta, Josef; Foret, František

    2015-01-01

    Roč. 15, č. 1 (2015), s. 311-318 ISSN 1473-0197 R&D Projects: GA ČR(CZ) GAP106/12/0522; GA ČR(CZ) GBP206/12/G014; GA MŠk(CZ) EE2.3.20.0182 Institutional support: RVO:68081715 Keywords : glass microchips * channel etching * supercritical water Subject RIV: CB - Analytical Chemistry, Separation Impact factor: 5.586, year: 2015

  9. Coiled tubing drilling with supercritical carbon dioxide

    Science.gov (United States)

    Kolle , Jack J.

    2002-01-01

    A method for increasing the efficiency of drilling operations by using a drilling fluid material that exists as supercritical fluid or a dense gas at temperature and pressure conditions existing at a drill site. The material can be used to reduce mechanical drilling forces, to remove cuttings, or to jet erode a substrate. In one embodiment, carbon dioxide (CO.sub.2) is used as the material for drilling within wells in the earth, where the normal temperature and pressure conditions cause CO.sub.2 to exist as a supercritical fluid. Supercritical carbon dioxide (SC--CO.sub.2) is preferably used with coiled tube (CT) drilling equipment. The very low viscosity SC--CO.sub.2 provides efficient cooling of the drill head, and efficient cuttings removal. Further, the diffusivity of SC--CO.sub.2 within the pores of petroleum formations is significantly higher than that of water, making jet erosion using SC--CO.sub.2 much more effective than water jet erosion. SC--CO.sub.2 jets can be used to assist mechanical drilling, for erosion drilling, or for scale removal. A choke manifold at the well head or mud cap drilling equipment can be used to control the pressure within the borehole, to ensure that the temperature and pressure conditions necessary for CO.sub.2 to exist as either a supercritical fluid or a dense gas occur at the drill site. Spent CO.sub.2 can be vented to the atmosphere, collected for reuse, or directed into the formation to aid in the recovery of petroleum.

  10. Computational Modeling of Supercritical and Transcritical Flows

    Science.gov (United States)

    2017-01-09

    Acentric factor I. Introduction Liquid rocket and gas turbine engines operate at high pressures . For gas turbines, the combustor pressurecan be 60 − 100...equation of state for several reduced pressures . The model captures the high density at very low temperatures and the supercritical behavior at high reduced...physical meaning. The temperature range over which the three roots are present is bounded by TL on the low side and TH on the high side. Figure 2: Roots

  11. Supercritical fluid extraction behaviour of polymer matrices

    International Nuclear Information System (INIS)

    Sujatha, K.; Kumar, R.; Sivaraman, N.; Srinivasan, T.G.; Vasudeva Rao, P.R.

    2007-01-01

    Organic compounds present in polymeric matrices such as neoprene, surgical gloves and PVC were co-extracted during the removal of uranium using supercritical fluid extraction (SFE) technique. Hence SFE studies of these matrices were carried out to establish the extracted species using HPLC, IR and mass spectrometry techniques. The initial study indicated that uranium present in the extract could be purified from the co-extracted organic species. (author)

  12. Advanced Thermal Storage for Central Receivers with Supercritical Coolants

    Energy Technology Data Exchange (ETDEWEB)

    Kelly, Bruce D.

    2010-06-15

    The principal objective of the study is to determine if supercritical heat transport fluids in a central receiver power plant, in combination with ceramic thermocline storage systems, offer a reduction in levelized energy cost over a baseline nitrate salt concept. The baseline concept uses a nitrate salt receiver, two-tank (hot and cold) nitrate salt thermal storage, and a subcritical Rankine cycle. A total of 6 plant designs were analyzed, as follows: Plant Designation Receiver Fluid Thermal Storage Rankine Cycle Subcritical nitrate salt Nitrate salt Two tank nitrate salt Subcritical Supercritical nitrate salt Nitrate salt Two tank nitrate salt Supercritical Low temperature H2O Supercritical H2O Two tank nitrate salt Supercritical High temperature H2O Supercritical H2O Packed bed thermocline Supercritical Low temperature CO2 Supercritical CO2 Two tank nitrate salt Supercritical High temperature CO2 Supercritical CO2 Packed bed thermocline Supercritical Several conclusions have been drawn from the results of the study, as follows: 1) The use of supercritical H2O as the heat transport fluid in a packed bed thermocline is likely not a practical approach. The specific heat of the fluid is a strong function of the temperatures at values near 400 °C, and the temperature profile in the bed during a charging cycle is markedly different than the profile during a discharging cycle. 2) The use of supercritical CO2 as the heat transport fluid in a packed bed thermocline is judged to be technically feasible. Nonetheless, the high operating pressures for the supercritical fluid require the use of pressure vessels to contain the storage inventory. The unit cost of the two-tank nitrate salt system is approximately $24/kWht, while the unit cost of the high pressure thermocline system is nominally 10 times as high. 3) For the supercritical fluids, the outer crown temperatures of the receiver tubes are in the range of 700 to 800 °C. At temperatures of 700 °C and above

  13. Fast infrared spectroscopy in supercritical fluids

    International Nuclear Information System (INIS)

    Sun, X.

    2000-05-01

    Chapter 1: Introduction. A brief introduction to supercritical fluids is given, illustrating why supercritical fluids are unique solvents and why there is a wide application of supercritical fluids in industry and laboratories. Potential ways for solvation in supercritical fluids to affect reactivity are briefly reviewed. A general introduction to the photochemistry of organometallic complexes is also given. Chapter 2: Time resolved vibrational spectroscopy. Time resolved resonance Raman is introduced and compared with Time-resolved infrared spectroscopy (TRIR). The different approaches of TRIR, including microsecond, nanosecond, and ultrafast (picosecond and femtosecond) systems are discussed. The advantages and disadvantages of these systems are also compared. The TRIR apparatus using an IR diode laser used for work in this thesis are described in detail. Experimental procedures for supercritical fluid TRIR experiments are described with emphasis on handling the IR cell for supercritical fluids and preparation of supercritical fluid solutions. Chapter 3: Photochemistry of group VIB hexacarbonyl compounds in supercritical noble gases and CO 2 solutions. A systematic TRIR study of the photolysis of M(CO) 6 in supercritical Ar, Kr, Xe, and CO 2 and the observation of M(CO) 5 L (M = Cr, Mo, and W; L = Ar (W only), Kr, Xe, and CO 2 ) is described. The second-order rate constants for the reaction of M(CO) 5 L with CO have been evaluated and the reactivity for each metal is Kr > Xe ∼ CO 2 . For M(CO) 5 Kr, M(CO) 5 Xe, or M(CO) 5 (CO 2 ), the reactivity is Cr ∼ Mo > W. In supercritical Kr doped with either Xe or CO 2 , the M(CO) 5 moiety interacts with Xe or CO 2 in preference to Kr. The effect of solvent density on the rate of the reaction of W(CO) 5 (CO 2 ) with CO has been investigated. The reaction of W(CO) 5 (CO 2 ) with CO in scCO 2 is predominantly a dissociative process. The activation energies for the reaction of W(CO) 5 Xe and W(CO) 5 (CO 2 ) with CO and

  14. Use of supercritical carbon dioxide extraction

    Energy Technology Data Exchange (ETDEWEB)

    Taniguchi, Masayuki (Niigata Univ., Faculty of Engineering, Niigata, (Japan))

    1989-09-25

    Supercritical fluid extraction is a novel diffusion and separation technique which exploits simultaneously the increase of vapor pressure and the difference of chemical affinities of fluids near the critical point. A solvent which is used as the supercritical fluid has the following features: the critical point exists in the position of relatively ease of handling, the solvent is applicable to the extraction of a physiological active substance of thermal instability. Carbon dioxide as the solvent is non-flammable, non-corrosive, non-toxic, cheap, and readily available of high purity. The results of studies on the use of supercritical carbon dioxide (SC-CO{sub 2}) as a solvent for natural products in the fermentation and food industries, were collected. SC-CO{sub 2} extraction are used in many fields, examples for the application are as follows: removal of organic solvents from antibiotics; extraction of vegetable oils contained in wheat germ oil, high quality mustard seeds, rice bran and so on; brewing of sake using rice and rice-koji; use as a non-aqueous medium for the synthesis of precursors of the Aspartame; and use in sterilization. 66 refs., 17 figs., 21 tabs.

  15. Engineering Escherichia coli for methanol conversion.

    Science.gov (United States)

    Müller, Jonas E N; Meyer, Fabian; Litsanov, Boris; Kiefer, Patrick; Potthoff, Eva; Heux, Stéphanie; Quax, Wim J; Wendisch, Volker F; Brautaset, Trygve; Portais, Jean-Charles; Vorholt, Julia A

    2015-03-01

    Methylotrophic bacteria utilize methanol and other reduced one-carbon compounds as their sole source of carbon and energy. For this purpose, these bacteria evolved a number of specialized enzymes and pathways. Here, we used a synthetic biology approach to select and introduce a set of "methylotrophy genes" into Escherichia coli based on in silico considerations and flux balance analysis to enable methanol dissimilation and assimilation. We determined that the most promising approach allowing the utilization of methanol was the implementation of NAD-dependent methanol dehydrogenase and the establishment of the ribulose monophosphate cycle by expressing the genes for hexulose-6-phosphate synthase (Hps) and 6-phospho-3-hexuloisomerase (Phi). To test for the best-performing enzymes in the heterologous host, a number of enzyme candidates from different donor organisms were selected and systematically analyzed for their in vitro and in vivo activities in E. coli. Among these, Mdh2, Hps and Phi originating from Bacillus methanolicus were found to be the most effective. Labeling experiments using (13)C methanol with E. coli producing these enzymes showed up to 40% incorporation of methanol into central metabolites. The presence of the endogenous glutathione-dependent formaldehyde oxidation pathway of E. coli did not adversely affect the methanol conversion rate. Taken together, the results of this study represent a major advancement towards establishing synthetic methylotrophs by gene transfer. Copyright © 2015 International Metabolic Engineering Society. Published by Elsevier Inc. All rights reserved.

  16. Evaluation of various Crown ethers for the supercritical fluid extraction of uranium from nitric acid medium

    International Nuclear Information System (INIS)

    Kumar, Pradeep; Rao, Ankita; Ramakumar, K.L.

    2009-01-01

    Various crowns have been evaluated for supercritical fluid extraction of uranium from nitric acid medium employing HPFOA as counter ion. Uranium extraction efficiency was found to be influenced by cavity size of crown ether and nature of substituents. Complexation tendency of UO 2 2+ increases with increasing cavity size of crown ether. Electron withdrawing substituents decreased the extraction efficiency which could be attributed to decrease in the basicity of four oxygen atoms and hence their bonding ability. Whereas electron donating substituents increased the efficiency due to increases in basicity of oxygen atoms and hence in increase in bonding ability. (author)

  17. Sorption phenomena of methanol on heat treated coal; Netsushori wo hodokoshita sekitan no methanol kyuchaku tokusei

    Energy Technology Data Exchange (ETDEWEB)

    Yasuda, H.; Kaiho, M.; Yamada, O.; Soneda, Y.; Kobayashi, M.; Makino, M. [National Institute for Resources and Environment, Tsukuba (Japan)

    1996-10-28

    Experiments were carried out to learn methanol sorption characteristics of heat-treated coal. When Taiheiyo coal is heat-treated at 125{degree}C, performed with a first methanol adsorption at 25{degree}C, and then desorption at 25{degree}C, a site with strong interaction with methanol and a site with relatively weak interaction are generated in test samples. A small amount of methanol remains in both sites. Then, when the methanol is desorbed at as low temperature as 70{degree}C, the methanol in the site with strong interaction remains as it has existed therein, but the methanol in the site with relatively weak interaction desorbs partially, hence the adsorption amount in a second adsorption at 25{degree}C increases. However, when desorption is performed at as high temperature as 125{degree}C, the methanol in the site with strong interaction also desorbs, resulting in increased adsorption heat in the second adsorption. The adsorption velocity drops, however. Existence of methanol in a site with strong interaction affects the adsorption velocity, but no effect is given by methanol in a site with weak interaction. 3 refs., 4 figs.

  18. Continuous production of biodiesel from microalgae by extraction coupling with transesterification under supercritical conditions.

    Science.gov (United States)

    Zhou, Dan; Qiao, Baoquan; Li, Gen; Xue, Song; Yin, Jianzhong

    2017-08-01

    Raw material for biodiesel has been expanded from edible oil to non-edible oil. In this study, biodiesel continuous production for two kinds of microalgae Chrysophyta and Chlorella sp. was conducted. Coupling with the supercritical carbon dioxide extraction, the oil of microalgae was extracted firstly, and then sent to the downstream production of biodiesel. The residue after decompression can be reused as the material for pharmaceuticals and nutraceuticals. Results showed that the particle size of microalgae, temperature, pressure, molar ration of methanol to oil, flow of CO 2 and n-hexane all have effects on the yield of biodiesel. With the optimal operation conditions: 40mesh algae, extraction temperature 60°C, flow of n-hexane 0.4ml/min, reaction temperature: 340°C, pressure: 18-20MPa, CO 2 flow of 0.5L/min, molar ration of methanol to oil 84:1, a yield of 56.31% was obtained for Chrysophyta, and 63.78% for Chlorella sp. due to the higher lipid content. Copyright © 2017. Published by Elsevier Ltd.

  19. Supercritical Carbon Dioxide Extraction of Bioactive Compounds from Ampelopsis grossedentata Stems: Process Optimization and Antioxidant Activity

    Directory of Open Access Journals (Sweden)

    Da Sun

    2011-10-01

    Full Text Available Supercritical carbon dioxide (SC-CO2 extraction of bioactive compounds including flavonoids and phenolics from Ampelopsis grossedentata stems was carried out. Extraction parameters such as pressure, temperature, dynamic time and modifier, were optimized using an orthogonal array design of L9 (34, and antioxidant activities of the extracts were evaluated by 2,2-diphenyl-1-picrylhydrazyl (DPPH free radical scavenging assay and ferrous ion chelating (FIC assay. The best conditions obtained for SC-CO2 extraction of flavonoids was 250 bar, 40 °C, 50 min, and with a modifier of methanol/ethanol (1:3, v/v, and that for phenolics extraction was 250 bar, 40 °C, 50 min, and with a modifier of methanol/ethanol (1:1, v/v. Meantime, flavonoids and phenolics were found to be mainly responsible for the DPPH scavenging activity of the extracts, but not for the chelating activity on ferrous ion according to Pearson correlation analysis. Furthermore, several unreported flavonoids such as apigenin, vitexin, luteolin, etc., have been detected in the extracts from A. grossedentata stems.

  20. Supercritical Fluid Extraction of Quinones from Compost for Microbial Community Analysis

    Directory of Open Access Journals (Sweden)

    Ni Luh Gede Ratna Juliasih

    2015-01-01

    Full Text Available Supercritical fluid extraction (SFE was used to extract quinones from compost to monitor the microbial community dynamics during composting. The 0.3 g of dried compost was extracted using 3 mL min−1 of carbon dioxide (90% and methanol (10% at 45°C and 25 MPa for a 30 min extraction time. The extracted quinones were analysed using ultra performance liquid chromatography (UPLC with 0.3 mL min−1 of methanol mobile phase for a 50 min chromatographic run time. A comparable detected amount of quinones was obtained using the developed method and an organic solvent extraction method, being 36.06 μmol kg−1 and 34.54 μmol kg−1, respectively. Significantly low value of dissimilarity index (D between the two methods (0.05 indicated that the quinone profile obtained by both methods was considered identical. The developed method was then applied to determine the maturity of the compost by monitoring the change of quinone during composting. The UQ-9 and MK-7 were predominant quinones in the initial stage of composting. The diversity of quinone became more complex during the cooling and maturation stages. This study showed that SFE had successfully extracted quinones from a complex matrix with simplification and rapidity of the analysis that is beneficial for routine analysis.

  1. Novel Anode Catalyst for Direct Methanol Fuel Cells

    Directory of Open Access Journals (Sweden)

    S. Basri

    2014-01-01

    Full Text Available PtRu catalyst is a promising anodic catalyst for direct methanol fuel cells (DMFCs but the slow reaction kinetics reduce the performance of DMFCs. Therefore, this study attempts to improve the performance of PtRu catalysts by adding nickel (Ni and iron (Fe. Multiwalled carbon nanotubes (MWCNTs are used to increase the active area of the catalyst and to improve the catalyst performance. Electrochemical analysis techniques, such as energy dispersive X-ray spectrometry (EDX, X-ray diffraction (XRD, field emission scanning electron microscopy (FESEM, and X-ray photoelectron spectroscopy (XPS, are used to characterize the kinetic parameters of the hybrid catalyst. Cyclic voltammetry (CV is used to investigate the effects of adding Fe and Ni to the catalyst on the reaction kinetics. Additionally, chronoamperometry (CA tests were conducted to study the long-term performance of the catalyst for catalyzing the methanol oxidation reaction (MOR. The binding energies of the reactants and products are compared to determine the kinetics and potential surface energy for methanol oxidation. The FESEM analysis results indicate that well-dispersed nanoscale (2–5 nm PtRu particles are formed on the MWCNTs. Finally, PtRuFeNi/MWCNT improves the reaction kinetics of anode catalysts for DMFCs and obtains a mass current of 31 A g−1 catalyst.

  2. Novel anode catalyst for direct methanol fuel cells.

    Science.gov (United States)

    Basri, S; Kamarudin, S K; Daud, W R W; Yaakob, Z; Kadhum, A A H

    2014-01-01

    PtRu catalyst is a promising anodic catalyst for direct methanol fuel cells (DMFCs) but the slow reaction kinetics reduce the performance of DMFCs. Therefore, this study attempts to improve the performance of PtRu catalysts by adding nickel (Ni) and iron (Fe). Multiwalled carbon nanotubes (MWCNTs) are used to increase the active area of the catalyst and to improve the catalyst performance. Electrochemical analysis techniques, such as energy dispersive X-ray spectrometry (EDX), X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), and X-ray photoelectron spectroscopy (XPS), are used to characterize the kinetic parameters of the hybrid catalyst. Cyclic voltammetry (CV) is used to investigate the effects of adding Fe and Ni to the catalyst on the reaction kinetics. Additionally, chronoamperometry (CA) tests were conducted to study the long-term performance of the catalyst for catalyzing the methanol oxidation reaction (MOR). The binding energies of the reactants and products are compared to determine the kinetics and potential surface energy for methanol oxidation. The FESEM analysis results indicate that well-dispersed nanoscale (2-5 nm) PtRu particles are formed on the MWCNTs. Finally, PtRuFeNi/MWCNT improves the reaction kinetics of anode catalysts for DMFCs and obtains a mass current of 31 A g(-1) catalyst.

  3. A gradient activation method for direct methanol fuel cells

    International Nuclear Information System (INIS)

    Liu, Guicheng; Yang, Zhaoyi; Halim, Martin; Li, Xinyang; Wang, Manxiang; Kim, Ji Young; Mei, Qiwen; Wang, Xindong; Lee, Joong Kee

    2017-01-01

    Highlights: • A gradient activation method was reported firstly for direct methanol fuel cells. • The activity recovery of Pt-based catalyst was introduced into the novel activation process. • The new activation method led to prominent enhancement of DMFC performance. • DMFC performance was improved with the novel activation step by step within 7.5 h. - Abstract: To realize gradient activation effect and recover catalytic activity of catalyst in a short time, a gradient activation method has firstly been proposed for enhancing discharge performance and perfecting activation mechanism of the direct methanol fuel cell (DMFC). This method includes four steps, i.e. proton activation, activity recovery activation, H_2-O_2 mode activation and forced discharging activation. The results prove that the proposed method has gradually realized replenishment of water and protons, recovery of catalytic activity of catalyst, establishment of transfer channels for electrons, protons, and oxygen, and optimization of anode catalyst layer for methanol transfer in turn. Along with the novel activation process going on, the DMFC discharge performance has been improved, step by step, to more than 1.9 times higher than that of the original one within 7.5 h. This method provides a practicable activation way for the real application of single DMFCs and stacks.

  4. Stability studies of oxytetracycline in methanol solution

    Science.gov (United States)

    Wang, Wei; Wu, Nan; Yang, Jinghui; Zeng, Ming; Xu, Chenshan; Li, Lun; Zhang, Meng; Li, Liting

    2018-02-01

    As one kind of typical tetracycline antibiotics, antibiotic residues of oxytetracycline have been frequently detected in many environmental media. In this study, the stability of oxytetracycline in methanol solution was investigated by high-performance liquid chromatography combined with UV-vis (HPLC-UV). The results show that the stability of oxytetracycline in methanol solution is highly related to its initial concentration and the preserved temperature. Under low temperature condition, the solution was more stable than under room temperature preservation. Under the same temperature preservation condition, high concentrations of stock solutions are more stable than low concentrations. The study provides a foundation for preserving the oxytetracycline-methanol solution.

  5. A rare presentation of methanol toxicity

    Directory of Open Access Journals (Sweden)

    Nikhil Gupta

    2013-01-01

    Full Text Available Methanol is a highly toxic alcohol resembling ethanol in smell and taste. Methanol poisoning is a lethal form of poisoning that can cause severe metabolic acidosis, visual disturbances, and neurological deficit. Brain lesions typically described in methanol toxicity are in the form of hemorrhagic and non-hemorrhagic necrosis of the basal ganglia and sub-cortical white matter. To our knowledge, lesions in the parietal, temporal, or frontal areas of cerebrum and cerebellar hemispheres have been rarely reported so far. We herewith report this rare presentation.

  6. Mechanism study of c.f.c Fe-Ni-Cr alloy corrosion in supercritical water

    International Nuclear Information System (INIS)

    Payet, M.

    2011-01-01

    Supercritical water can be use as a high pressure coolant in order to improve the thermodynamic efficiency of power plants. For nuclear concept, lifetime is an important safety parameter for materials. Thus materials selection criteria concern high temperature yield stress, creep resistance, resistance to irradiation embrittlement and also to both uniform corrosion and stress corrosion cracking.This study aims for supplying a new insight on uniform corrosion mechanism of Fe-Ni-Cr f.c.c. alloys in deaerated supercritical water at 600 C and 25 MPa. Corrosion tests were performed on 316L and 690 alloys as sample autoclaves taking into account the effect of surface finishes. Morphologies, compositions and crystallographic structure of the oxides were determined using FEG scanning electron microscopy, glow discharge spectroscopy and X-ray diffraction. If supercritical water is expected to have a gas-like behaviour in the test conditions, the results show a significant dissolution of the alloy species. Thus the corrosion in supercritical water can be considered similar to corrosion in under-critical water assuming the higher temperature and its effect on the solid state diffusion. For alloy 690, the protective oxide layer formed on polished surface consists of a chromia film topped with an iron and nickel mixed chromite or spinel. The double oxide layer formed on 316L steel seems less protective with an outer porous layer of magnetite and an inhomogeneous Cr-rich inner layer. For each alloy, the study of the inner protective scale growth mechanisms by marker or tracer experiments reveals that diffusion in the oxide scale is governed by an anionic process. However, surface finishes impact deeply the growth mechanisms. Comparisons between the results for the steel suggest that there is a competition between the oxidation of iron and chromium in supercritical water. Sufficient available chromium is required in order to form a thin oxide layer. Highly deformed or ultra fine

  7. Channel type reactors with supercritical water coolant. Russian experience

    International Nuclear Information System (INIS)

    Kuznetsov, Y.N.; Gabaraev, B.A.

    2003-01-01

    Transition to coolant of supercritical parameters allows for principle engineering-andeconomic characteristics of light-water nuclear power reactors to be substantially enhanced. Russian experience in development of channel-type reactors with supercritical water coolant has demonstrated advantages and practical feasibility of such reactors. (author)

  8. Thermodynamic Optimization of Supercritical CO{sub 2} Brayton Cycles

    Energy Technology Data Exchange (ETDEWEB)

    Rhim, Dong-Ryul; Park, Sung-Ho; Kim, Su-Hyun; Yeom, Choong-Sub [Institute for Advanced Engineering, Yongin (Korea, Republic of)

    2015-05-15

    The supercritical CO{sub 2} Brayton cycle has been studied for nuclear applications, mainly for one of the alternative power conversion systems of the sodium cooled fast reactor, since 1960's. Although the supercritical CO{sub 2} Brayton cycle has not been expected to show higher efficiency at lower turbine inlet temperature over the conventional steam Rankine cycle, the higher density of supercritical CO{sub 2} like a liquid in the supercritical region could reduce turbo-machinery sizes, and the potential problem of sodium-water reaction with the sodium cooled fast reactor might be solved with the use of CO{sub 2} instead of water. The supercritical CO{sub 2} recompression Brayton cycle was proposed for the better thermodynamic efficiency than for the simple supercritical CO{sub 2} Brayton cycle. Thus this paper presents the efficiencies of the supercritical CO{sub 2} recompression Brayton cycle along with several decision variables for the thermodynamic optimization of the supercritical CO{sub 2} recompression Brayton cycle. The analytic results in this study show that the system efficiency reaches its maximum value at a compressor outlet pressure of 200 bars and a recycle fraction of 30 %, and the lower minimum temperature approach at the two heat exchangers shows higher system efficiency as expected.

  9. Electronics

    Science.gov (United States)

    2001-01-01

    International Acer Incorporated, Hsin Chu, Taiwan Aerospace Industrial Development Corporation, Taichung, Taiwan American Institute of Taiwan, Taipei, Taiwan...Singapore and Malaysia .5 - 4 - The largest market for semiconductor products is the high technology consumer electronics industry that consumes up...Singapore, and Malaysia . A new semiconductor facility costs around $3 billion to build and takes about two years to become operational

  10. World scale fuel methanol facility siting

    International Nuclear Information System (INIS)

    Stapor, M.C.; Hederman, W.F.

    1990-01-01

    Since the Administration announced a clean alternative fuels initiative, industry and government agencies' analyses of the economics of methanol as an alternative motor vehicle fuel have accelerated. In the short run, methanol appears attractive because excess production capacity currently has depressed methanol prices and marginal costs of production are lower than other fuels (current excess capacity). In the long run, however, full costs are the more relevant. To lower average production costs, U.S. policy interest has focused on production from a world-scale, 10,000 tons per day (tpd) methanol plant facility on a foreign site. This paper reviews several important site and financial considerations in a framework to evaluate large scale plant development. These considerations include: risks associated with a large process plant; supply economics of foreign sites; and investment climates and financial incentives for foreign investment at foreign sites

  11. Regulatory aspects of methanol metabolism in yeasts

    International Nuclear Information System (INIS)

    Trotsenko, Y.A.; Bystrykh, L.V.; Ubiyvovk, V.M.

    1984-01-01

    Formaldehyde is the first and key intermediate in the metabolism of methylotrophic yeasts since it stands at a branch point of pathways for methanol oxidation and assimilation. Methanol and, formaldehyde are toxic compounds which severely affect the growth rate, yield coefficient, etc., of yeasts. Two questions arise when considering regulation of methanol metabolism in yeasts how a nontoxic level of formaldehyde is maintained in the cell and how the formaldehyde flow is distributed into oxidation and assimilation. To answer these questions we studied the role of GSH, which spontaneously binds formaldehyde, yielding S-hydroxymethylglutathione; in vivo rates of formaldehyde dissimilation and assimilation by using [ 14 C]methanol; profiles of enzymes responsible for production and utilization of formaldehyde; and levels of metabolites affecting dissimilation and assimilation of formaldehyde. All of the experiments were carried out with the methylotrophic yeast Candida boidinii KD1. 19 refs., 4 figs., 1 tab

  12. Advances in direct oxidation methanol fuel cells

    Science.gov (United States)

    Surampudi, S.; Narayanan, S. R.; Vamos, E.; Frank, H.; Halpert, G.; Laconti, Anthony B.; Kosek, J.; Prakash, G. K. Surya; Olah, G. A.

    1993-01-01

    Fuel cells that can operate directly on fuels such as methanol are attractive for low to medium power applications in view of their low weight and volume relative to other power sources. A liquid feed direct methanol fuel cell has been developed based on a proton exchange membrane electrolyte and Pt/Ru and Pt catalyzed fuel and air/O2 electrodes, respectively. The cell has been shown to deliver significant power outputs at temperatures of 60 to 90 C. The cell voltage is near 0.5 V at 300 mA/cm(exp 2) current density and an operating temperature of 90 C. A deterrent to performance appears to be methanol crossover through the membrane to the oxygen electrode. Further improvements in performance appear possible by minimizing the methanol crossover rate.

  13. Phytochemical screening and antiproliferative effects of methanol ...

    African Journals Online (AJOL)

    Preliminary Phytochemical screening. Thin layer chromatographic profile (TLC) of methanol crude extract and antiproliferative studies were carried out in this research. Phytochemical screening revealed the presence of carbohydrate, glycoside, anthraquinone, steroid, triterpenes, saponin, tannins, flavonoids and alkaloid.

  14. Biological Properties of Fucoxanthin in Oil Recovered from Two Brown Seaweeds Using Supercritical CO2 Extraction

    Directory of Open Access Journals (Sweden)

    Saravana Periaswamy Sivagnanam

    2015-05-01

    Full Text Available The bioactive materials in brown seaweeds hold great interest for developing new drugs and healthy foods. The oil content in brown seaweeds (Saccharina japonica and Sargassum horneri was extracted by using environmentally friendly supercritical CO2 (SC-CO2 with ethanol as a co-solvent in a semi-batch flow extraction process and compared the results with a conventional extraction process using hexane, ethanol, and acetone mixed with methanol (1:1, v/v. The SC-CO2 method was used at a temperature of 45 °C and pressure of 250 bar. The flow rate of CO2 (27 g/min was constant for the entire extraction period of 2 h. The obtained oil from the brown seaweeds was analyzed to determine their valuable compounds such as fatty acids, phenolic compounds, fucoxanthin and biological properties including antioxidant, antimicrobial, and antihypertension effects. The amounts of fucoxanthin extracted from the SC-CO2 oils of S. japonica and S. horneri were 0.41 ± 0.05 and 0.77 ± 0.07 mg/g, respectively. High antihypertensive activity was detected when using mixed acetone and methanol, whereas the phenolic content and antioxidant property were higher in the oil extracted by SC-CO2. The acetone–methanol mix extracts exhibited better antimicrobial activities than those obtained by other means. Thus, the SC-CO2 extraction process appears to be a good method for obtaining valuable compounds from both brown seaweeds, and showed stronger biological activity than that obtained by the conventional extraction process.

  15. Biological Properties of Fucoxanthin in Oil Recovered from Two Brown Seaweeds Using Supercritical CO2 Extraction.

    Science.gov (United States)

    Sivagnanam, Saravana Periaswamy; Yin, Shipeng; Choi, Jae Hyung; Park, Yong Beom; Woo, Hee Chul; Chun, Byung Soo

    2015-05-29

    The bioactive materials in brown seaweeds hold great interest for developing new drugs and healthy foods. The oil content in brown seaweeds (Saccharina japonica and Sargassum horneri) was extracted by using environmentally friendly supercritical CO2 (SC-CO2) with ethanol as a co-solvent in a semi-batch flow extraction process and compared the results with a conventional extraction process using hexane, ethanol, and acetone mixed with methanol (1:1, v/v). The SC-CO2 method was used at a temperature of 45 °C and pressure of 250 bar. The flow rate of CO2 (27 g/min) was constant for the entire extraction period of 2 h. The obtained oil from the brown seaweeds was analyzed to determine their valuable compounds such as fatty acids, phenolic compounds, fucoxanthin and biological properties including antioxidant, antimicrobial, and antihypertension effects. The amounts of fucoxanthin extracted from the SC-CO2 oils of S. japonica and S. horneri were 0.41 ± 0.05 and 0.77 ± 0.07 mg/g, respectively. High antihypertensive activity was detected when using mixed acetone and methanol, whereas the phenolic content and antioxidant property were higher in the oil extracted by SC-CO2. The acetone-methanol mix extracts exhibited better antimicrobial activities than those obtained by other means. Thus, the SC-CO2 extraction process appears to be a good method for obtaining valuable compounds from both brown seaweeds, and showed stronger biological activity than that obtained by the conventional extraction process.

  16. Simultaneous determination of inorganic anions and cations by supercritical fluid chromatography using evaporative light scattering detection.

    Science.gov (United States)

    Foulon, Catherine; Di Giulio, Pauline; Lecoeur, Marie

    2018-01-26

    Supercritical fluid chromatography (SFC) is commonly used for the analysis of non-polar compounds, but remains poorly explored for the separation of polar and ionized molecules. In this paper, SFC has been investigated for the separation of 14 inorganic ions sampled in aqueous solutions. Four polar stationary phases were first screened using CO 2 -methanol-based mobile phases containing water or different acidic or basic additives, in order to select the most efficient conditions for the simultaneous retention of inorganic cations and anions and to favor their detection using evaporative light scattering detector (ELSD). Orthogonal selectivity was obtained depending on the stationary phase used: whereas anions are less retained on HILIC stationary phase, 2-ethylpyridine (2-EP) stationary phase exhibits strong interaction for anions. Best results were obtained under gradient elution mode using a 2-EP stationary phase and by adding 0.2% triethylamine in the CO 2 -methanol-based mobile phase. The composition of the injection solvent was also investigated. The results showed that a methanolic sample containing a percentage of water not exceeding 20% does not affect the analytical performances obtained on 2-EP. Moreover, the presence of triethylamine in the injection solvent contributes to eliminate peaks shoulders. Among the 14 inorganic ions tested, three cations (Li + , Ca 2+ and Mg 2+ ) and five anions (Cl - , Br - , NO 3 - , I - , SCN - ) were totally resolved in 15 min. NO 3 - and NO 2 - still coeluted in the final optimized conditions. The other investigated ions were either strongly retained on the stationary phase or not detected by the ELSD. Copyright © 2017 Elsevier B.V. All rights reserved.

  17. 27.12 MHz plasma generation in supercritical carbon dioxide

    International Nuclear Information System (INIS)

    Kawashima, Ayato; Toyota, Hiromichi; Nomura, Shinfuku; Takemori, Toshihiko; Mukasa, Shinobu; Maehara, Tsunehiro; Yamashita, Hiroshi

    2007-01-01

    An experiment was conducted for generating high-frequency plasma in supercritical carbon dioxide; it is expected to have the potential for applications in various types of practical processes. It was successfully generated at 6-20 MPa using electrodes mounted in a supercritical cell with a gap of 1 mm. Emission spectra were then measured to investigate the physical properties of supercritical carbon dioxide plasma. The results indicated that while the emission spectra for carbon dioxide and carbon monoxide could be mainly obtained at a low pressure, the emission spectra for atomic oxygen could be obtained in the supercritical state, which increased with the pressure. The temperature of the plasma in supercritical state was estimated to be approximately 6000-7000 K on the assumption of local thermodynamic equilibrium and the calculation results of thermal equilibrium composition in this state showed the increase of atomic oxygen by the decomposition of CO 2

  18. Introduction to supercritical fluids a spreadsheet-based approach

    CERN Document Server

    Smith, Richard; Peters, Cor

    2013-01-01

    This text provides an introduction to supercritical fluids with easy-to-use Excel spreadsheets suitable for both specialized-discipline (chemistry or chemical engineering student) and mixed-discipline (engineering/economic student) classes. Each chapter contains worked examples, tip boxes and end-of-the-chapter problems and projects. Part I covers web-based chemical information resources, applications and simplified theory presented in a way that allows students of all disciplines to delve into the properties of supercritical fluids and to design energy, extraction and materials formation systems for real-world processes that use supercritical water or supercritical carbon dioxide. Part II takes a practical approach and addresses the thermodynamic framework, equations of state, fluid phase equilibria, heat and mass transfer, chemical equilibria and reaction kinetics of supercritical fluids. Spreadsheets are arranged as Visual Basic for Applications (VBA) functions and macros that are completely (source code) ...

  19. Simulation of Thermal Hydraulic at Supercritical Pressures with APROS

    Energy Technology Data Exchange (ETDEWEB)

    Kurki, Joona [VTT Technical Research Centre of Finland, P.O. Box 1000, FI02044 VTT (Finland)

    2008-07-01

    The proposed concepts for the fourth generation of nuclear reactors include a reactor operating with water at thermodynamically supercritical state, the Supercritical Water Reactor (SCWR). For the design and safety demonstrations of such a reactor, the possibility to accurately simulate the thermal hydraulics of the supercritical coolant is an absolute prerequisite. For this purpose, the one-dimensional two-phase thermal hydraulics solution of APROS process simulation software was developed to function at the supercritical pressure region. Software modifications included the redefinition of some parameters that have physical significance only at the subcritical pressures, improvement of the steam tables, and addition of heat transfer and friction correlations suitable for the supercritical pressure region. (author)

  20. Supercritical fluid extraction of 2-alkylcyclobutanones formed from triglycerides by irradiation

    International Nuclear Information System (INIS)

    Horvatovich, P.; Farkas, J.; Hasselmann, C.; Marchioni, E.

    1998-01-01

    Complete text of publication follows. Radiation processing is employed to improve the microbiological safety of foodstuffs, and at the same time to suit the 'minimal processing' principle. However adequate information for consumers to enable their free choices requires specific detection methods of irradiation processes. For this purpose one of the most suitable methods is the detection of 2-alkylcyclobutanones which are formed - according to the present knowledge - only by irradiation from the fatty acid part of triglycerides. For detection of these compounds a European Norm (EN 1785) has been established. The method consists of Sohxlet extraction of fatty acids from the food sample, separation of 2-alkylcyclobutanones from other fatty components with liquid chromatography on Florisil TM , and the GC-MS analysis of the appropriate fraction with single ion monitoring (SIM) monitoring of 98 and 112 ions. But this method has a relatively high detection limit (∼1 kGy), it is time consuming and needs costly and sophisticated apparates. To improve the detection of 2-alkylcyclobutanones we replaced the Sohxlet extraction step with a supercritical fluid extraction. We optimised trapping and extraction parameters. It was found that supercritical fluid extraction is more selective than Sohxlet extraction used in the standard protocol. The extract obtained by supercritical fluid extraction contains less quantity and number of detection-disturbing components. This work is the first step towards decreasing the detection limit which will be the derivatization of 2-alkylcyclobutanones with halogen-containing reagent, and detection of derivatives with electron-capture detector (ECD)

  1. Methanol plant ship: Appendix. Export trade information

    International Nuclear Information System (INIS)

    1988-01-01

    The document is an appendix to the final report on a proposed methanol plant ship off of the coast of Trinidad. The document incorporates the results of the redetermination of capital required to implement the project. It also presents a revised cost analysis, with better accuracy, for the project. The projected operating revenues and revised expenses are also given. As a continuation of the information presented in the final report, the methanol market and proposed products are discussed in the report

  2. Comparative Neuropharmacological Activities Methanolic Extracts of ...

    African Journals Online (AJOL)

    Comparative neuropharmacological efficacy of the leaf and root 70 % methanol extract of Cissus cornifolia was studied in mice. The extractive values of the leaf and root methanol extract was found to be 31.5 g with yield of 12.6 %(w/w) and 37.8 g with the yield of 15.12 %(w/w) respectively. The acute toxicity (LD50) values ...

  3. Temperature and pressure effects on solubility in supercritical carbon dioxide and retention in supercritical fluid chromatography

    NARCIS (Netherlands)

    Lou, X.W.; Janssen, J.G.M.; Cramers, C.A.M.G.

    1997-01-01

    Solubilities of some polycyclic aromatic hydrocarbons (PAHs) in supercritical carbon dioxide were measured with a procedure based on a direct on-line combination of a saturation cell to a flame ionization detector. Acenaphthene, anthrance and chrysene were selected as the test solutes. A method was

  4. Vacuum-ultraviolet (VUV) photoionization of small methanol and methanol-water clusters

    International Nuclear Information System (INIS)

    Ahmed, Musahid; Ahmed, Musahid; Wilson, Kevin R.; Belau, Leonid; Kostko, Oleg

    2008-01-01

    In this work we report on the vacuum-ultraviolet (VUV) photoionization of small methanol and methanol-water clusters. Clusters of methanol with water are generated via co-expansion of the gas phase constituents in a continuous supersonic jet expansion of methanol and water seeded in Ar. The resulting clusters are investigated by single photon ionization with tunable vacuum ultraviolet synchrotron radiation and mass analyzed using reflectron mass spectrometry. Protonated methanol clusters of the form (CH3OH)nH + (n=1-12) dominate the mass spectrum below the ionization energy of the methanol monomer. With an increase in water concentration, small amounts of mixed clusters of the form (CH3OH)n(H2O)H + (n=2-11) are detected. The only unprotonated species observed in this work are the methanol monomer and dimer. Appearance energies are obtained from the photoionization efficiency (PIE) curves for CH3OH +, (CH 3OH)2 +, (CH3OH)nH + (n=1-9), and (CH 3OH)n(H2O)H + (n=2-9 ) as a function of photon energy. With an increase in the water content in the molecular beam, there is an enhancement of photoionization intensity for methanol dimer and protonated methanol monomer at threshold. These results are compared and contrasted to previous experimental observations

  5. Methanol-Tolerant Cathode Catalyst Composite For Direct Methanol Fuel Cells

    Science.gov (United States)

    Zhu, Yimin; Zelenay, Piotr

    2006-03-21

    A direct methanol fuel cell (DMFC) having a methanol fuel supply, oxidant supply, and its membrane electrode assembly (MEA) formed of an anode electrode and a cathode electrode with a membrane therebetween, a methanol oxidation catalyst adjacent the anode electrode and the membrane, an oxidant reduction catalyst adjacent the cathode electrode and the membrane, comprises an oxidant reduction catalyst layer of a platinum-chromium alloy so that oxidation at the cathode of methanol that crosses from the anode through the membrane to the cathode is reduced with a concomitant increase of net electrical potential at the cathode electrode.

  6. Transesterification of waste vegetable oil under pulse sonication using ethanol, methanol and ethanol–methanol mixtures

    Energy Technology Data Exchange (ETDEWEB)

    Martinez-Guerra, Edith; Gude, Veera Gnaneswar, E-mail: gude@cee.msstate.edu

    2014-12-15

    Highlights: • Pulse sonication effect on transesterification of waste vegetable oil was studied. • Effects of ethanol, methanol, and alcohol mixtures on FAMEs yield were evaluated. • Effect of ultrasonic intensity, power density, and its output rates were evaluated. • Alcohol mixtures resulted in higher biodiesel yields due to better solubility. - Abstract: This study reports on the effects of direct pulse sonication and the type of alcohol (methanol and ethanol) on the transesterification reaction of waste vegetable oil without any external heating or mechanical mixing. Biodiesel yields and optimum process conditions for the transesterification reaction involving ethanol, methanol, and ethanol–methanol mixtures were evaluated. The effects of ultrasonic power densities (by varying sample volumes), power output rates (in W), and ultrasonic intensities (by varying the reactor size) were studied for transesterification reaction with ethanol, methanol and ethanol–methanol (50%-50%) mixtures. The optimum process conditions for ethanol or methanol based transesterification reaction of waste vegetable oil were determined as: 9:1 alcohol to oil ratio, 1% wt. catalyst amount, 1–2 min reaction time at a power output rate between 75 and 150 W. It was shown that the transesterification reactions using ethanol–methanol mixtures resulted in biodiesel yields as high as >99% at lower power density and ultrasound intensity when compared to ethanol or methanol based transesterification reactions.

  7. Integrated anode structure for passive direct methanol fuel cells with neat methanol operation

    Science.gov (United States)

    Wu, Huijuan; Zhang, Haifeng; Chen, Peng; Guo, Jing; Yuan, Ting; Zheng, Junwei; Yang, Hui

    2014-02-01

    A microporous titanium plate based integrated anode structure (Ti-IAS) suitable for passive direct methanol fuel cells (DMFCs) fueled with neat methanol is reported. This anode structure incorporates a porous titanium plate as a methanol mass transfer barrier and current collector, pervaporation film for passively vaporizing methanol, vaporous methanol cavity for evenly distributing fuel, and channels for carbon dioxide venting. With the effective control of methanol delivery rate, the Ti-IAS based DMFC allows the direct use of neat methanol as the fuel source. In the meantime, the required water for methanol-oxidation reaction at the anode can also be fully recovered from the cathode with the help of the highly hydrophobic microporous layer in the cathode. DMFCs incorporating this new anode structure exhibit a power density as high as 40 mW cm-2 and a high volumetric energy density of 489 Wh L-1 operating with neat methanol and at 25 °C. Importantly, no obvious performance degradation of the passive DMFC system is observed after more than 90 h of continuous operation. The experimental results reveal that the compact DMFC based on the Ti-IAS exhibits a substantial potential as power sources for portable applications.

  8. Correlation of supercritical-fluid extraction recoveries with supercritical-fluid chromatographic retention data: A fundamental study

    NARCIS (Netherlands)

    Lou, X.W.; Janssen, J.G.M.; Cramers, C.A.M.G.

    1995-01-01

    The possibility of using supercritical-fluid chromatographic retention data for examining the effects of operational parameters, such as pressure and flow rate, on the extraction characteristics in supercritical-fluid extraction (SFE) was investigated. A model was derived for calculating the

  9. Direct synthesis of few-layer graphene supported platinum nanocatalyst for methanol oxidation

    Science.gov (United States)

    Tan, Hong; Ma, Xiaohui; Sheng, Leimei; An, Kang; Yu, Liming; Zhao, Hongbin; Xu, Jiaqiang; Ren, Wei; Zhao, Xinluo

    2014-11-01

    High-crystalline few-layer graphene supported Pt nanoparticles have been synthesized by arc discharge evaporation of carbon electrodes containing Pt element. A high-temperature treatment under hydrogen atmosphere has been carried out to obtain a new type of Pt/graphene catalyst for methanol oxidation in direct methanol fuel cell. The morphology and structure characterizations of as-grown few-layer graphene supported Pt nanoparticles and Pt/graphene catalysts have been studied by Raman spectroscopy, scanning electron microscopy with energy-dispersive spectroscopy, and high-resolution transmission electron microscopy. Cyclic voltammograms and chronoamperometric curves show that our present Pt/graphene catalysts have larger current density for methanol oxidation, higher tolerance to carbon monoxide poisoning, and better stability during the operating procedure, compared to commercial Pt/C catalysts.

  10. Measurements of convective heat transfer to vertical upward flows of CO{sub 2} in circular tubes at near-critical and supercritical pressures

    Energy Technology Data Exchange (ETDEWEB)

    Zahlan, H., E-mail: hussamzahlan@gmail.com [Canadian Nuclear Laboratories, Chalk River, K0J 1J0 (Canada); Department of Mechanical Engineering, University of Ottawa, Ottawa, ON K1N 6N5 (Canada); Groeneveld, D. [Canadian Nuclear Laboratories, Chalk River, K0J 1J0 (Canada); Department of Mechanical Engineering, University of Ottawa, Ottawa, ON K1N 6N5 (Canada); Tavoularis, S. [Department of Mechanical Engineering, University of Ottawa, Ottawa, ON K1N 6N5 (Canada)

    2015-08-15

    downstream sections of the tubes. The collected data were reduced and compiled. The reported heat transfer database consists of more than 17,000 data points in the 8 and 22 mm tubes, along with pressure drop data for the 8 mm tube. The tables of heat transfer and pressure drop data are provided as separate files in electronic format. The results are presented in plots of wall temperature and heat transfer coefficient vs. bulk fluid enthalpy. The parametric trends of diameter, mass flux, pressure and heat flux on these wall temperature and heat transfer coefficient profiles have been plotted and discussed. The present supercritical heat transfer measurements are in good agreement with corresponding results reported by other investigators.

  11. Development of a Crosslinked Pore-filling Membrane with an Extremely Low Swelling Ratio and Methanol Crossover for Direct Methanol Fuel Cells

    International Nuclear Information System (INIS)

    Li, Yunxi; Hoorfar, Mina; Shen, Kuizhi; Fang, Jiyong; Yue, Xigui; Jiang, Zhenhua

    2017-01-01

    A poly (ether sulphone)-based pore-filling membrane was successfully fabricated and tested against a conventional Nafion-based membrane in direct methanol fuel cells. An amino-containing polymer with a low degree of sulphonation (DS) was synthesized and used as the supporting substrate. The porous substrate was prepared by introducing the porogenic agent (tetrafluoroborate) into the membrane casting solution. The effects of the content of the porogenic agent on the pore morphologies were evaluated using field emission scanning electron microscopy. Then, an epoxy resin was introduced into the porous electrolyte for the first time to minimize the swelling and methanol crossover that resulted from the high degree of sulphonation. In essence, solidification of the amino groups in the substrate results in 3D crosslinking of epoxy resins, which greatly suppresses the swelling and methanol crossover of the composite membranes with enhanced mechanical properties and enhances the thermal and oxidation stability compared to Nafion 117. The resulting composite membrane also shows high proton conductivity that is only slightly lower than that of Nafion 117. However, the selectivity between the proton conductivity and methanol permeability is higher for the composite membranes than that of Nafion 117. The composite membrane also shows a better performance in single cell tests with 10 M methanol.

  12. Modelling and experimental studies on a direct methanol fuel cell working under low methanol crossover and high methanol concentrations

    Energy Technology Data Exchange (ETDEWEB)

    Oliveira, V.B.; Pinto, A.M.F.R. [Centro de Estudos de Fenomenos de Transporte, Departamento de Eng. Quimica, Faculdade de Engenharia da Universidade do Porto, Rua Dr. Roberto Frias, 4200-465 Porto (Portugal); Rangel, C.M. [Instituto Nacional de Energia e Geologia, Fuel Cells and Hydrogen, Estrada do Paco do Lumiar, 1649-038 Lisboa (Portugal)

    2009-08-15

    A number of issues need to be resolved before DMFC can be commercially viable such as the methanol crossover and water crossover which must be minimised in portable DMFCs. The main gain of this work is to systematically vary commercial MEA materials and check their influence on the cell performance of a direct methanol fuel cell operating at close to room temperature. A detailed experimental study on the performance of an <> developed DMFC with 25 cm{sup 2} of active membrane area, working near the ambient conditions is described. Tailored MEAs (membrane-electrode assemblies), with different structures and combinations of gas diffusion layers (GDLs), were designed and tested in order to select optimal working conditions at high methanol concentration levels without sacrificing performance. The experimental polarization and power density curves were successfully compared with the predictions of a steady state, one-dimensional model accounting for coupled heat and mass transfer, along with the electrochemical reactions occurring in the DMFC recently developed by the same authors. The influence of the anode gas diffusion layer media, the membrane thickness and the MEA properties on the cell performance are explained under the light of the predicted methanol crossover rate across the membrane. A tailored MEA build-up with the common available commercial materials was proposed to achieve relatively low methanol crossover, operating at high methanol concentrations. The use of adequate materials for the gas diffusion layers (carbon paper at the anode GDL and carbon cloth at the cathode GDL) enables the use of thinner membranes enhancing the water back diffusion which is essential to work at high methanol concentrations. (author)

  13. Microwave-Assisted Synthesis of Co3(PO42 Nanospheres for Electrocatalytic Oxidation of Methanol in Alkaline Media

    Directory of Open Access Journals (Sweden)

    Prabhakarn Arunachalam

    2017-04-01

    Full Text Available Low-cost and high-performance advanced electrocatalysts for direct methanol fuel cells are of key significance for the improvement of environmentally-pleasant energy technologies. Herein, we report the facile synthesis of cobalt phosphate (Co3(PO42 nanospheres by a microwave-assisted process and utilized as an electrocatalyst for methanol oxidation. The phase formation, morphological surface structure, elemental composition, and textural properties of the synthesized (Co3(PO42 nanospheres have been examined by powder X-ray diffraction (XRD, Fourier transform-infrared spectroscopy (FT-IR, field emission-scanning electron microscopy (FE-SEM, high-resolution transmission electron microscopy (HRTEM, X-ray photoelectron spectroscopy (XPS, and nitrogen adsorption-desorption isotherm investigations. The performance of an electrocatalytic oxidation of methanol over a Co3(PO42 nanosphere-modified electrode was evaluated in an alkaline solution using cyclic voltammetry (CV and chronopotentiometry (CP techniques. Detailed studies were made for the methanol oxidation by varying the experimental parameters, such as catalyst loading, methanol concentration, and long-term stability for the electro-oxidation of methanol. The good electrocatalytic performances of Co3(PO42 should be related to its good surface morphological structure and high number of active surface sites. The present investigation illustrates the promising application of Co3(PO42 nanospheres as a low-cost and more abundant electrocatalyst for direct methanol fuel cells.

  14. Production of methanol/DME from biomass

    Energy Technology Data Exchange (ETDEWEB)

    Ahrenfeldt, J.; Birk Henriksen, U.; Muenster-Swendsen, J.; Fink, A.; Roengaard Clausen, L.; Munkholt Christensen, J.; Qin, K.; Lin, W.; Arendt Jensen, P.; Degn Jensen, A.

    2011-07-01

    In this project the production of DME/methanol from biomass has been investigated. Production of DME/methanol from biomass requires the use of a gasifier to transform the solid fuel to a synthesis gas (syngas) - this syngas can then be catalytically converted to DME/methanol. Two different gasifier types have been investigated in this project: 1) The Two-Stage Gasifier (Viking Gasifier), designed to produce a very clean gas to be used in a gas engine, has been connected to a lab-scale methanol plant, to prove that the gas from the gasifier could be used for methanol production with a minimum of gas cleaning. This was proved by experiments. Thermodynamic computer models of DME and methanol plants based on using the Two-Stage Gasification concept were created to show the potential of such plants. The models showed that the potential biomass to DME/methanol + net electricity energy efficiency was 51-58% (LHV). By using waste heat from the plants for district heating, the total energy efficiencies could reach 87-88% (LHV). 2) A lab-scale electrically heated entrained flow gasifier has been used to gasify wood and straw. Entrained flow gasifiers are today the preferred gasifier type for commercial coal gasification, but little information exists on using these types of gasifiers for biomass gasification. The experiments performed provided quantitative data on product and gas composition as a function of operation conditions. Biomass can be gasified with less oxygen consumption compared to coal. The organic fraction of the biomass that is not converted to gas appears as soot. Thermodynamic computer models of DME and methanol plants based on using entrained flow gasification were created to show the potential of such plants. These models showed that the potential torrefied biomass to DME/methanol + net electricity energy efficiency was 65-71% (LHV). Different routes to produce liquid transport fuels from biomass are possible. They include production of RME (rapeseed oil

  15. Short-term inhalation toxicity of methanol, gasoline, and methanol/gasoline in the rat.

    Science.gov (United States)

    Poon, R; Chu, I; Bjarnason, S; Vincent, R; Potvin, M; Miller, R B; Valli, V E

    1995-01-01

    Four- to five-week-old male and female Sprague Dawley rats were exposed to vapors of methanol (2500 ppm), gasoline (3200 ppm), and methanol/gasoline (2500/3200 ppm, 570/3200 ppm) six hours per day, five days per week for four weeks. Control animals were exposed to filtered room air only. Depression in body weight gain and reduced food consumption were observed in male rats, and increased relative liver weight was detected in rats of both sexes exposed to gasoline or methanol/gasoline mixtures. Rats of both sexes exposed to methanol/gasoline mixtures had increased relative kidney weight and females exposed to gasoline and methanol/gasoline mixtures had increased kidney weight. Decreased serum glucose and cholesterol were detected in male rats exposed to gasoline and methanol/gasoline mixtures. Decreased hemoglobin was observed in females inhaling vapors of gasoline and methanol/gasoline at 570/3200 ppm. Urine from rats inhaling gasoline or methanol/gasoline mixtures had up to a fourfold increase in hippuric acid, a biomarker of exposure to the toluene constituent of gasoline, and up to a sixfold elevation in ascorbic acid, a noninvasive biomarker of hepatic response. Hepatic mixed-function oxidase (aniline hydroxylase, aminopyrine N-demethylase and ethoxyresorufin O-deethylase) activities and UDP-glucuronosyltransferase activity were elevated in rats exposed to gasoline and methanol/gasoline mixtures. Histopathological changes were confined to very mild changes in the nasal passages and in the uterus, where decreased incidence or absence of mucosal and myometrial eosinophilia was observed in females inhaling gasoline and methanol/gasoline at 570/3200 ppm. It was concluded that gasoline was largely responsible for the adverse effects, the most significant of which included depression in weight gain in the males, increased liver weight and hepatic microsomal enzyme activities in both sexes, and suppression of uterine eosinophilia. No apparent interactive effects

  16. Supercritical nonlinear parametric dynamics of Timoshenko microbeams

    Science.gov (United States)

    Farokhi, Hamed; Ghayesh, Mergen H.

    2018-06-01

    The nonlinear supercritical parametric dynamics of a Timoshenko microbeam subject to an axial harmonic excitation force is examined theoretically, by means of different numerical techniques, and employing a high-dimensional analysis. The time-variant axial load is assumed to consist of a mean value along with harmonic fluctuations. In terms of modelling, a continuous expression for the elastic potential energy of the system is developed based on the modified couple stress theory, taking into account small-size effects; the kinetic energy of the system is also modelled as a continuous function of the displacement field. Hamilton's principle is employed to balance the energies and to obtain the continuous model of the system. Employing the Galerkin scheme along with an assumed-mode technique, the energy terms are reduced, yielding a second-order reduced-order model with finite number of degrees of freedom. A transformation is carried out to convert the second-order reduced-order model into a double-dimensional first order one. A bifurcation analysis is performed for the system in the absence of the axial load fluctuations. Moreover, a mean value for the axial load is selected in the supercritical range, and the principal parametric resonant response, due to the time-variant component of the axial load, is obtained - as opposed to transversely excited systems, for parametrically excited system (such as our problem here), the nonlinear resonance occurs in the vicinity of twice any natural frequency of the linear system; this is accomplished via use of the pseudo-arclength continuation technique, a direct time integration, an eigenvalue analysis, and the Floquet theory for stability. The natural frequencies of the system prior to and beyond buckling are also determined. Moreover, the effect of different system parameters on the nonlinear supercritical parametric dynamics of the system is analysed, with special consideration to the effect of the length-scale parameter.

  17. Towards neat methanol operation of direct methanol fuel cells: a novel self-assembled proton exchange membrane.

    Science.gov (United States)

    Li, Jing; Cai, Weiwei; Ma, Liying; Zhang, Yunfeng; Chen, Zhangxian; Cheng, Hansong

    2015-04-18

    We report here a novel proton exchange membrane with remarkably high methanol-permeation resistivity and excellent proton conductivity enabled by carefully designed self-assembled ionic conductive channels. A direct methanol fuel cell utilizing the membrane performs well with a 20 M methanol solution, very close to the concentration of neat methanol.

  18. Supercritical-pressure light water cooled reactors

    CERN Document Server

    Oka, Yoshiaki

    2014-01-01

    This book focuses on the latest reactor concepts, single pass core and experimental findings in thermal hydraulics, materials, corrosion, and water chemistry. It highlights research on supercritical-pressure light water cooled reactors (SCWRs), one of the Generation IV reactors that are studied around the world. This book includes cladding material development and experimental findings on heat transfer, corrosion and water chemistry. The work presented here will help readers to understand the fundamental elements of reactor design and analysis methods, thermal hydraulics, materials and water

  19. Bedforms formed by experimental supercritical density flows

    Science.gov (United States)

    Naruse, Hajime; Izumi, Norihiro; Yokokawa, Miwa; Muto, Tetsuji

    2014-05-01

    This study reveals characteristics and formative conditions of bedforms produced by saline density flows in supercritical flow conditions, especially focusing on the mechanism of the formation of plane bed. The motion of sediment particles forming bedforms was resolved by high-speed cameras (1/1000 frame/seconds). Experimental density flows were produced by mixtures of salt water (1.01-1.04 in density) and plastic particles (1.5 in specific density, 140 or 240 mm in diameter). Salt water and plastic particles are analogue materials of muddy water and sand particles in turbidity currents respectively. Acrylic flume (4.0 m long, 2.0 cm wide and 0.5 m deep) was submerged in an experimental tank (6.0 m long, 1.8 m wide and 1.2 m deep) that was filled by clear water. Features of bedforms were observed when the bed state in the flume reached equilibrium condition. The experimental conditions range 1.5-4.2 in densimetric Froude number and 0.2-0.8 in Shields dimensionless stress. We report the two major discoveries as a result of the flume experiments: (1) Plane bed under Froude-supercritical flows and (2) Geometrical characteristics of cyclic steps formed by density flows. (1) Plane bed was formed under the condition of supercritical flow regime. In previous studies, plane bed has been known to be formed by subcritical unidirectional flows (ca. 0.8 in Froude number). However, this study implies that plane bed can also be formed by supercritical conditions with high Shields dimensionless stress (>0.4) and very high Froude number (> 4.0). This discovery may suggest that previous estimations of paleo-hydraulic conditions of parallel lamination in turbidites should be reconsidered. The previous experimental studies and data from high-speed camera suggest that the region of plane bed formation coincides with the region of the sheet flow developments. The particle transport in sheet flow (thick bedload layer) induces transform of profile of flow shear stress, which may be

  20. Thermodynamic analysis of a supercritical water reactor

    International Nuclear Information System (INIS)

    Edwards, M.

    2007-01-01

    A thermodynamic model has been developed for a hypothetical design of a Supercritical Water Reactor, with emphasis on Canadian design criteria. The model solves for cycle efficiency, mass flows and physical conditions throughout the plant based on input parameters of operating pressures and efficiencies of components. The model includes eight feedwater heaters, three feedwater pumps, a deaerator, a condenser, the core, three turbines and two reheaters. To perform the calculations, Microsoft Excel was used in conjunction with FLUIDCAL-IAPWS95 and VBA code. The calculations show that a thermal efficiency of 47.5% can be achieved with a core outlet temperature of 625 o C. (author)

  1. Preparative isolation and purification of hainanmurpanin, meranzin, and phebalosin from leaves of Murraya exotica L. using supercritical fluid extraction combined with consecutive high-speed countercurrent chromatography.

    Science.gov (United States)

    Yan, Rongwei; Shen, Jie; Liu, Xiaojing; Zou, Yong; Xu, Xinjun

    2018-05-01

    The objective of this study was to develop a consecutive preparation method for the isolation and purification of hainanmurpanin, meranzin, and phebalosin from leaves of Murraya exotica L. The process involved supercritical fluid extraction with CO 2 , solvent extraction, and two-step high-speed countercurrent chromatography. Pressure, temperature, and the volume of entrainer were optimized as 27 MPa, 52°C, and 60 mL by response surface methodology in supercritical fluid extraction with CO 2 , and the yield of the crude extracts was 7.91 g from 100 g of leaves. Subsequently, 80% methanol/water was used to extract and condense the three compounds from the crude extracts, and 4.23 g of methanol/water extracts was obtained. Then, a two-step high-speed countercurrent chromatography procedure was developed for the isolation of the three target compounds from methanol/water extracts, including conventional high-speed countercurrent chromatography for further enrichment and consecutive high-speed countercurrent chromatography for purification. The yield of concentrates from high-speed countercurrent chromatography was 2.50 g from 4.23 g of methanol/water extracts. Finally, the consecutive high-speed countercurrent chromatography produced 103.2 mg of hainanmurpanin, 244.7 mg of meranzin, and 255.4 mg of phebalosin with purities up to 97.66, 99.36, and 98.64%, respectively, from 900 mg of high-speed countercurrent chromatography concentrates in one run of three consecutive sample loadings without exchanging a solvent system. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. A selective electrocatalyst-based direct methanol fuel cell operated at high concentrations of methanol.

    Science.gov (United States)

    Feng, Yan; Liu, Hui; Yang, Jun

    2017-06-01

    Owing to the serious crossover of methanol from the anode to the cathode through the polymer electrolyte membrane, direct methanol fuel cells (DMFCs) usually use dilute methanol solutions as fuel. However, the use of high-concentration methanol is highly demanded to improve the energy density of a DMFC system. Instead of the conventional strategies (for example, improving the fuel-feed system, membrane development, modification of electrode, and water management), we demonstrate the use of selective electrocatalysts to run a DMFC at high concentrations of methanol. In particular, at an operating temperature of 80°C, the as-fabricated DMFC with core-shell-shell Au@Ag 2 S@Pt nanocomposites at the anode and core-shell Au@Pd nanoparticles at the cathode produces a maximum power density of 89.7 mW cm -2 at a methanol feed concentration of 10 M and maintains good performance at a methanol concentration of up to 15 M. The high selectivity of the electrocatalysts achieved through structural construction accounts for the successful operation of the DMFC at high concentrations of methanol.

  3. A selective electrocatalyst–based direct methanol fuel cell operated at high concentrations of methanol

    Science.gov (United States)

    Feng, Yan; Liu, Hui; Yang, Jun

    2017-01-01

    Owing to the serious crossover of methanol from the anode to the cathode through the polymer electrolyte membrane, direct methanol fuel cells (DMFCs) usually use dilute methanol solutions as fuel. However, the use of high-concentration methanol is highly demanded to improve the energy density of a DMFC system. Instead of the conventional strategies (for example, improving the fuel-feed system, membrane development, modification of electrode, and water management), we demonstrate the use of selective electrocatalysts to run a DMFC at high concentrations of methanol. In particular, at an operating temperature of 80°C, the as-fabricated DMFC with core-shell-shell Au@Ag2S@Pt nanocomposites at the anode and core-shell Au@Pd nanoparticles at the cathode produces a maximum power density of 89.7 mW cm−2 at a methanol feed concentration of 10 M and maintains good performance at a methanol concentration of up to 15 M. The high selectivity of the electrocatalysts achieved through structural construction accounts for the successful operation of the DMFC at high concentrations of methanol. PMID:28695199

  4. Methanol utilizing Desulfotomaculum species utilizes hydrogen in a methanol-fed sulfate-reducing bioreactor

    NARCIS (Netherlands)

    Balk, M.; Weijma, J.; Goorissen, H.P.; Ronteltap, M.; Hansen, T.A.; Stams, A.J.M.

    2007-01-01

    A sulfate-reducing bacterium, strain WW1, was isolated from a thermophilic bioreactor operated at 65 degrees C with methanol as sole energy source in the presence of sulfate. Growth of strain WW1 on methanol or acetate was inhibited at a sulfide concentration of 200 mg l(-1), while on H-2/CO2, no

  5. Supercritical water natural circulation flow stability experiment research

    Energy Technology Data Exchange (ETDEWEB)

    Ma, Dongliang; Zhou, Tao; Li, Bing [North China Electric Power Univ., Beijing (China). School of Nuclear Science and Engineering; North China Electric Power Univ., Beijing (China). Inst. of Nuclear Thermalhydraulic Safety and Standardization; North China Electric Power Univ., Beijing (China). Beijing Key Lab. of Passive Safety Technology for Nuclear Energy; Huang, Yanping [Nuclear Power Institute of China, Chengdu (China). Science and Technology on Reactor System Design Technology Lab.

    2017-12-15

    The Thermal hydraulic characteristics of supercritical water natural circulation plays an important role in the safety of the Generation-IV supercritical water-cooled reactors. Hence it is crucial to conduct the natural circulation heat transfer experiment of supercritical water. The heat transfer characteristics have been studied under different system pressures in the natural circulation systems. Results show that the fluctuations in the subcritical flow rate (for natural circulation) is relatively small, as compared to the supercritical flow rate. By increasing the heating power, it is observed that the amplitude (and time period) of the fluctuation tends to become larger for the natural circulation of supercritical water. This tends to show the presence of flow instability in the supercritical water. It is possible to observe the flow instability phenomenon when the system pressure is suddenly reduced from the supercritical pressure state to the subcritical state. At the test outlet section, the temperature is prone to increase suddenly, whereas the blocking effect may be observed in the inlet section of the experiment.

  6. Development of a test facility for analyzing supercritical fluid blowdown

    International Nuclear Information System (INIS)

    Roberto, Thiago D.; Alvim, Antonio C.M.

    2015-01-01

    The generation IV nuclear reactors under development mostly use supercritical fluids as the working fluid because higher temperatures improve the thermal efficiency. Supercritical fluids are used by modern nuclear power plants to achieve thermal efficiencies of around 45%. With water as the supercritical working fluid, these plants operate at a high temperature and pressure. However, experiments on supercritical water are limited by technical and financial difficulties. These difficulties can be overcome by using model fluids, which have more feasible supercritical conditions and exhibit a lower critical pressure and temperature. Experimental research is normally used to determine the conditions under which model fluids represent supercritical fluids under steady-state conditions. A fluid-to-fluid scaling approach has been proposed to determine model fluids that can represent supercritical fluids in a transient state. This paper presents an application of fractional scale analysis to determine the simulation parameters for a depressurization test facility. Carbon dioxide (CO 2 ) and R134a gas were considered as the model fluids because their critical point conditions are more feasible than those of water. The similarities of water (prototype), CO 2 (model) and R134a (model) for depressurization in a pressure vessel were analyzed. (author)

  7. Study on photocatalysis of TiO2 nanotubes prepared by methanol ...

    Indian Academy of Sciences (India)

    TiO2 nanotubes were synthesized by the solvothermal process at low temperature in a highly alkaline water–methanol mixed solution. Their characteristics were identified by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), specific surface area (BET), Fourier transform infrared spectroscopy (FTIR) ...

  8. Quantifying the promotion of Cu catalysts by ZnO for methanol synthesis

    DEFF Research Database (Denmark)

    Kuld, Sebastian; Thorhauge, Max; Falsig, Hanne

    2016-01-01

    Promoter elements enhance the activity and selectivity of heterogeneous catalysts. Here, we show how methanol synthesis from synthesis gas over copper (Cu) nanoparticles is boosted by zinc oxide (ZnO) nanoparticles. By combining surface area titration, electron microscopy, activity measurement, d...

  9. Zircon Supported Copper Catalysts for the Steam Reforming of Methanol

    Science.gov (United States)

    Widiastri, M.; Fendy, Marsih, I. N.

    2008-03-01

    Steam reforming of methanol (SRM) is known as one of the most favorable catalytic processes for producing hydrogen. Current research on zirconia, ZrO2 supported copper catalyst revealed that CuO/ZrO2 as an active catalyst for the SRM. Zircon, ZrSiO4 is available from the by-product of tin mining. In the work presented here, the catalytic properties of CuO/ZrSiO4 with various copper oxide compositions ranging from 2.70% (catalyst I), 4.12% (catalyst II), and 7.12%-mass (catalyst III), synthesized by an incipient wetness impregnation technique, were investigated to methanol conversion, selectivity towards CO formation, and effect of ZnO addition (7.83%CuO/8.01%ZnO/ZrSiO4 = catalyst V). The catalytic activity was obtained using a fixed bed reactor and the zircon supported catalyst activity was compared to those of CuO/ZnO/Al2O3 catalyst (catalyst IV) and commercial Kujang LTSC catalyst. An X-ray powder diffraction (XRD) analysis was done to identify the abundant phases of the catalysts. The catalysts topography and particle diameter were measured with scanning electron microscopy (SEM) and composition of the catalysts was measured by SEM-EDX, scanning electron microscope-energy dispersive using X-ray analysis. The results of this research provide information on the possibility of using zircon (ZrSiO4) as solid support for SRM catalysts.

  10. Effects of Supercritical Environment on Hydrocarbon-fuel Injection

    Institute of Scientific and Technical Information of China (English)

    Bongchul Shin; Dohun Kim; Min Son; Jaye Koo

    2017-01-01

    In this study,the effects of environment conditions on decane were investigated.Decane was injected in subcritical and supercritical ambient conditions.The visualization chamber was pressurized to 1.68 MPa by using nitrogen gas at a temperature of 653 K for subcritical ambient conditions.For supercritical ambient conditions,the visualization chamber was pressurized to 2.52 MPa by using helium at a temperature of 653 K.The decane injection in the pressurized chamber was visualized via a shadowgraph technique and gradient images were obtained by a post processing method.A large variation in density gradient was observed at jet interface in the case of subcritical injection in subcritical ambient conditions.Conversely,for supercritical injection in supercritical ambient conditions,a small density gradient was observed at the jet interface.In a manner similar to that observed in other cases,supercritical injection in subcritical ambient conditions differed from supercritical ambient conditions such as sphere shape liquid.Additionally,there were changes in the interface,and the supercritical injection core width was thicker than that in the subcritical injection.Furthermore,in cases with the same injection conditions,the change in the supercritical ambient normalized core width was smaller than the change in the subcritical ambient normalized core width owing to high specific heat at the supercritical injection and small phase change at the interface.Therefore,the interface was affected by the changing ambient condition.Given that the effect of changing the thermodynamic properties of propellants could be essential for a variable thrust rocket engine,the effects of the ambient conditions were investigated experimentally.

  11. Effects of supercritical environment on hydrocarbon-fuel injection

    Science.gov (United States)

    Shin, Bongchul; Kim, Dohun; Son, Min; Koo, Jaye

    2017-04-01

    In this study, the effects of environment conditions on decane were investigated. Decane was injected in subcritical and supercritical ambient conditions. The visualization chamber was pressurized to 1.68 MPa by using nitrogen gas at a temperature of 653 K for subcritical ambient conditions. For supercritical ambient conditions, the visualization chamber was pressurized to 2.52 MPa by using helium at a temperature of 653 K. The decane injection in the pressurized chamber was visualized via a shadowgraph technique and gradient images were obtained by a post processing method. A large variation in density gradient was observed at jet interface in the case of subcritical injection in subcritical ambient conditions. Conversely, for supercritical injection in supercritical ambient conditions, a small density gradient was observed at the jet interface. In a manner similar to that observed in other cases, supercritical injection in subcritical ambient conditions differed from supercritical ambient conditions such as sphere shape liquid. Additionally, there were changes in the interface, and the supercritical injection core width was thicker than that in the subcritical injection. Furthermore, in cases with the same injection conditions, the change in the supercritical ambient normalized core width was smaller than the change in the subcritical ambient normalized core width owing to high specific heat at the supercritical injection and small phase change at the interface. Therefore, the interface was affected by the changing ambient condition. Given that the effect of changing the thermodynamic properties of propellants could be essential for a variable thrust rocket engine, the effects of the ambient conditions were investigated experimentally.

  12. Methanol from biomass by partial oxidation

    International Nuclear Information System (INIS)

    Anon.

    1989-01-01

    The advantages of methanol should grow when petroleum again becomes scarce and expensive. An active program should be continued to develop technology and resolve outstanding questions. Some of the elements of this program included in this paper are: Make design studies and more accurate cost estimates for the largest plant. The increased size of this plant over the small plant studied by S and W should result in improved methanol yield and better energy efficiency. Continue development of the SERI biomass gasifier for a better understanding of design and operating parameters, for design of larger units, for higher operating pressures, and for gasification of Hawaiian woods and agricultural wastes. An earlier gasifier test bed in Hawaii is very desirable. Develop a plan to build successfully larger methanol plants in Hawaii to provide the basis for a large plant. Develop a plan for large-scale production of biomass in the islands. Elements of the plan might include technical (types of trees, maximizing wood per acre, and harvesting processes), economic (price to be paid for the biomass), social, cultural, and political factors. Develop a plan to convert liquid fuel users to methanol and begin implementing the plan as the initial small plants supply methanol. Develop an overall plant to integrate the various parts of the program covered above

  13. Neutron scattering study of dilute supercritical solutions

    International Nuclear Information System (INIS)

    Cochran, H.D.; Wignall, G.D.; Shah, V.M.; Londono, J.D.; Bienkowski, P.R.

    1994-01-01

    Dilute solutions in supercritical solvents exhibit interesting microstructures that are related to their dramatic macroscopic behavior. In typical attractive solutions, solutes are believed to be surrounded by clusters of solvent molecules, and solute molecules are believed to congregate in the vicinity of one another. Repulsive solutions, on the other hand, exhibit a local region of reduced solvent density around the solute with solute-solute congregation. Such microstructures influence solubility, partial molar volume, reaction kinetics, and many other properties. We have undertaken to observe these interesting microstructures directly by neutron scattering experiments on dilute noble gas systems including Ar. The three partial structure factors for such systems and the corresponding pair correlation functions can be determined by using the isotope substitution technique. The systems studied are uniquely suited for our objectives because of the large coherent neutron scattering length of the isotope 36 Ar and because of the accurate potential energy functions that are available for use in molecular simulations and theoretical calculations to be compared with the scattering results. We will describe our experiment, the unique apparatus we have built for it, and the neutron scattering results from our initial allocations of beam time. We will also describe planned scattering experiments to follow those with noble gases, including study of long-chain molecules in supercritical solvents. Such studies will involve hydrocarbon mixtures with and without deuteration to provide contrast

  14. Oxidation of oily sludge in supercritical water

    International Nuclear Information System (INIS)

    Cui Baochen; Cui Fuyi; Jing Guolin; Xu Shengli; Huo Weijing; Liu Shuzhi

    2009-01-01

    The oxidation of oily sludge in supercritical water is performed in a batch reactor at reaction temperatures between 663 and 723 K, the reaction times between 1 and 10 min and pressure between 23 and 27 MPa. Effect of reaction parameters such as reaction time, temperature, pressure, O 2 excess and initial COD on oxidation of oily sludge is investigated. The results indicate that chemical oxygen demand (COD) removal rate of 92% can be reached in 10 min. COD removal rate increases as the reaction time, temperature and initial COD increase. Pressure and O 2 excess have no remarkable affect on reaction. By taking into account the dependence of reaction rate on COD concentration, a global power-law rate expression was regressed from experimental data. The resulting pre-exponential factor was 8.99 x 10 14 (mol L -1 ) -0.405 s -1 ; the activation energy was 213.13 ± 1.33 kJ/mol; and the reaction order for oily sludge (based on COD) is 1.405. It was concluded that supercritical water oxidation (SCWO) is a rapidly emerging oily sludge processing technology.

  15. Supercritical water oxidation treatment of textile sludge.

    Science.gov (United States)

    Zhang, Jie; Wang, Shuzhong; Li, Yanhui; Lu, Jinling; Chen, Senlin; Luo, XingQi

    2017-08-01

    In this work, we studied the supercritical water oxidation (SCWO) of the textile sludge, the hydrothermal conversion of typical textile compounds and the corrosion properties of stainless steel 316. Moreover, the influence mechanisms of NaOH during these related processes were explored. The results show that decomposition efficiency for organic matter in liquid phase of the textile sludge was improved with the increment of reaction temperature or oxidation coefficient. However, the organic substance in solid phase can be oxidized completely in supercritical water. Serious coking occurred during the high pressure water at 250-450°C for the Reactive Orange 7, while at 300 and 350°C for the polyvinyl alcohol. The addition of NaOH not only accelerated the destruction of organic contaminants in the SCWO reactor, but effectively inhibited the dehydration conversion of textile compounds during the preheating process, which was favorable for the treatment system of textile sludge. The corrosion experiment results indicate that the stainless steel 316 could be competent for the body materials of the reactor and the heat exchangers. Furthermore, there was prominent enhancement of sodium hydroxide for the corrosion resistance of 316 in subcritical water. On the contrary the effect was almost none during SCWO.

  16. Supercritical Extraction Process of Allspice Essential Oil

    Directory of Open Access Journals (Sweden)

    Yasvet Y. Andrade-Avila

    2017-01-01

    Full Text Available Allspice essential oil was extracted with supercritical carbon dioxide (SC-CO2 in a static process at three different temperatures (308.15, 313.15, and 318.15 K and four levels of pressure (100, 200, 300, and 360 bar. The amount of oil extracted was measured at intervals of 1, 2, 3, 4, 5, and 6 h; the most extraction yield reached was of 68.47% at 318.15 K, 360 bar, and 6 h of contact time. In this supercritical extraction process, the distribution coefficient (KD, the mean effective diffusion coefficient (Def, the energy of activation (Ea, the thermodynamic properties (ΔG0, ΔH0, and ΔS0, and the apparent solubility (S expressed as mass fraction (w/w were evaluated for the first time. At the equilibrium the experimental apparent solubility data were successfully correlated with the modified Chrastil equation.

  17. Supercritical extraction of oleaginous: parametric sensitivity analysis

    Directory of Open Access Journals (Sweden)

    Santos M.M.

    2000-01-01

    Full Text Available The economy has become universal and competitive, thus the industries of vegetable oil extraction must advance in the sense of minimising production costs and, at the same time, generating products that obey more rigorous patterns of quality, including solutions that do not damage the environment. The conventional oilseed processing uses hexane as solvent. However, this solvent is toxic and highly flammable. Thus the search of substitutes for hexane in oleaginous extraction process has increased in the last years. The supercritical carbon dioxide is a potential substitute for hexane, but it is necessary more detailed studies to understand the phenomena taking place in such process. Thus, in this work a diffusive model for semi-continuous (batch for the solids and continuous for the solvent isothermal and isobaric extraction process using supercritical carbon dioxide is presented and submitted to a parametric sensitivity analysis by means of a factorial design in two levels. The model parameters were disturbed and their main effects analysed, so that it is possible to propose strategies for high performance operation.

  18. Modern supercritical fluid technology for food applications.

    Science.gov (United States)

    King, Jerry W

    2014-01-01

    This review provides an update on the use of supercritical fluid (SCF) technology as applied to food-based materials. It advocates the use of the solubility parameter theory (SPT) for rationalizing the results obtained when employing sub- and supercritical media to food and nutrient-bearing materials and for optimizing processing conditions. Total extraction and fractionation of foodstuffs employing SCFs are compared and are illustrated by using multiple fluids and unit processes to obtain the desired food product. Some of the additional prophylactic benefits of using carbon dioxide as the processing fluid are explained and illustrated with multiple examples of commercial products produced using SCF media. I emphasize the role of SCF technology in the context of environmentally benign and sustainable processing, as well as its integration into an overall biorefinery concept. Conclusions are drawn in terms of current trends in the field and future research that is needed to secure new applications of the SCF platform as applied in food science and technology.

  19. Ion mobility spectrometry after supercritical fluid chromatography

    International Nuclear Information System (INIS)

    Morrissey, M.A.

    1988-01-01

    In this work, a Fourier transform ion mobility spectrometer (FT-IMS) was constructed and evaluated as a detector for supercritical fluid chromatography (SFC). The FT-IMS provides both quantitative and qualitative data of a wide range of compounds, selective and nonselective modes of chromatographic detection, and it is compatible with a wide range of SFC mobile phases. Drift spectra are presented for a number of samples, including polymers, lipids, herbicides, antibiotics, and pharmaceuticals. The unique properties of supercritical fluids made it possible to introduce these compounds into the spectrometer. While the drift spectra presented are generally simple, showing only a quasi-molecular ion, a few are surprising complex. Examples of selective and non-selective detection demonstrate the usefulness of the detector. Examples are presented for fish oil concentrate, bacon grease extract, soil extract, and polymer mixtures. In the case of Triton X-100, a non-ionic surfactant, the FT-IMS was able to selectively detect individual oligomers in the polymer mixture. In the case of a polydimethylsilicone mixture the detector isolated a contaminant in the mixture

  20. High Density Thermal Energy Storage with Supercritical Fluids

    Science.gov (United States)

    Ganapathi, Gani B.; Wirz, Richard

    2012-01-01

    A novel approach to storing thermal energy with supercritical fluids is being investigated, which if successful, promises to transform the way thermal energy is captured and utilized. The use of supercritical fluids allows cost-affordable high-density storage with a combination of latent heat and sensible heat in the two-phase as well as the supercritical state. This technology will enhance penetration of several thermal power generation applications and high temperature water for commercial use if the overall cost of the technology can be demonstrated to be lower than the current state-of-the-art molten salt using sodium nitrate and potassium nitrate eutectic mixtures.

  1. Selective free radical reactions using supercritical carbon dioxide.

    Science.gov (United States)

    Cormier, Philip J; Clarke, Ryan M; McFadden, Ryan M L; Ghandi, Khashayar

    2014-02-12

    We report herein a means to modify the reactivity of alkenes, and particularly to modify their selectivity toward reactions with nonpolar reactants (e.g., nonpolar free radicals) in supercritical carbon dioxide near the critical point. Rate constants for free radical addition of the light hydrogen isotope muonium to ethylene, vinylidene fluoride, and vinylidene chloride in supercritical carbon dioxide are compared over a range of pressures and temperatures. Near carbon dioxide's critical point, the addition to ethylene exhibits critical speeding up, while the halogenated analogues display critical slowing. This suggests that supercritical carbon dioxide as a solvent may be used to tune alkene chemistry in near-critical conditions.

  2. Experimental study on the liquefaction of cellulose in supercritical ethanol

    Science.gov (United States)

    Peng, Jinxing; Liu, Xinyuan; Bao, Zhenbo

    2018-03-01

    Cellulose is the major composition of solid waste for producing biofuel; cellulose liquefaction is helpful for realizing biomass supercritical liquefaction process. This paper is taking supercritical ethanol as the medium, liquefied cellulose with the intermittence installation of high press cauldron. Experiments have studied technical condition and the technology parameter of cellulose liquefaction in supercritical ethanol, and the pyrolysis mechanism was analysed based on the pyrolysis product. Results show that cellulose can be liquefied, can get good effect through appropriate technology condition. Under not catalyst, highest liquefaction rate of cellulose can reach 73.5%. The composition of the pyrolysis product was determined by GC-MS.

  3. Materials challenges for the supercritical water-cooled reactor (SCWR)

    International Nuclear Information System (INIS)

    Baindur, S.

    2008-01-01

    This paper discusses the materials requirements of the Supercritical Water-cooled Reactor (SCWR) which arise from its severe expected operating conditions: (i) Outlet Temperature (to 650 C); (ii) Pressure of 25 MPa for the coolant containment, (iii) Thermochemical stress in the presence of supercritical water, and (iv) Radiative damage (up to 150 dpa for the fast spectrum variant). These operating conditions are reviewed; the phenomenology of materials in the supercritical water environment that create the materials challenges is discussed; knowledge gaps are identified, and efforts to understand material behaviour under the operating conditions expected in the SCWR are described. (author)

  4. Investigation of unstable periodic space-time states in distributed active system with supercritical current

    International Nuclear Information System (INIS)

    Koronovskij, A.A.; Rempen, I.S.; Khramov, A.E.

    2003-01-01

    The set of the unstable periodic space-time states, characterizing the chaotic space-time dynamics of the electron beam with the supercritical current in the Pierce diode is discussed. The Lyapunov indicators of the revealed instable space-time states of the chaotic dynamics of the distributed self-excited system are calculated. It is shown that change in the set of the unstable periodic states in dependence on the Pierce parameter is determined by change in the various orbits stability, which is demonstrated by the values of senior Lyapunov unstable state index [ru

  5. Determination of coumarins in the roots of Angelica dahurica by supercritical fluid chromatography.

    Science.gov (United States)

    Pfeifer, Isabella; Murauer, Adele; Ganzera, Markus

    2016-09-10

    The fact that supercritical fluid chromatography (SFC) offers many desirable features is known for a long time. Yet, the number of applications on natural products is still limited, because robust and user-friendly instrumentation became available just a few years ago. As coumarins hardly have been studied by this technique we developed the first SFC assay for their determination in crude plant material. After method optimization eight standard compounds, including simple coumarins, linear and angular furanocoumarins, could be baseline separated in 6min using an Acquity UPC(2) CSH Fluoro-Phenyl 1.7μm column with supercritical CO2, methanol and diethylamine as mobile phase. Method validation confirmed that the assay is linear (R(2)≥0.9995), precise (intra-day variation≤5.8%; inter-day variation≤4.4%) and accurate (recovery rates from 96.5 to 104.2%). Detection limits determined at 300nm were below 2ng on-column, and the method showed to be well suited for the analysis of coumarins in Angelica dahurica roots. It was observed that qualitative as well as quantitative composition vary significantly. In all samples Imperatorin (0.09-0.28%) was the major coumarin, followed either by Isoimperatorin or Oxypeucedanin; the total coumarin content ranged from 0.16 to 0.77%. The results were in good agreement to published data, so that because of its speed and green nature SFC is definitely an interesting alternative for the analysis of this important class of natural products. Copyright © 2016 Elsevier B.V. All rights reserved.

  6. Improved Anode for a Direct Methanol Fuel Cell

    Science.gov (United States)

    Valdez, Thomas; Narayanan, Sekharipuram

    2005-01-01

    A modified chemical composition has been devised to improve the performance of the anode of a direct methanol fuel cell. The main feature of the modified composition is the incorporation of hydrous ruthenium oxide into the anode structure. This modification can reduce the internal electrical resistance of the cell and increase the degree of utilization of the anode catalyst. As a result, a higher anode current density can be sustained with a smaller amount of anode catalyst. These improvements can translate into a smaller fuel-cell system and higher efficiency of conversion. Some background information is helpful for understanding the benefit afforded by the addition of hydrous ruthenium oxide. The anode of a direct methanol fuel cell sustains the electro-oxidation of methanol to carbon dioxide in the reaction CH3OH + H2O--->CO2 + 6H(+) + 6e(-). An electrocatalyst is needed to enable this reaction to occur. The catalyst that offers the highest activity is an alloy of approximately equal numbers of atoms of the noble metals platinum and ruthenium. The anode is made of a composite material that includes high-surface-area Pt/Ru alloy particles and a proton-conducting ionomeric material. This composite is usually deposited onto a polymer-electrolyte (proton-conducting) membrane and onto an anode gas-diffusion/current-collector sheet that is subsequently bonded to the proton-conducting membrane by hot pressing. Heretofore, the areal density of noble-metal catalyst typically needed for high performance has been about 8 mg/cm2. However, not all of the catalyst has been utilized in the catalyzed electro-oxidation reaction. Increasing the degree of utilization of the catalyst would make it possible to improve the performance of the cell for a given catalyst loading and/or reduce the catalyst loading (thereby reducing the cost of the cell). The use of carbon and possibly other electronic conductors in the catalyst layer has been proposed for increasing the utilization of the

  7. Preparation of silver nanoparticles/graphene nanosheets as a catalyst for electrochemical oxidation of methanol

    Energy Technology Data Exchange (ETDEWEB)

    Han, Kun; Miao, Peng; Tang, Yuguo, E-mail: tangyg@sibet.ac.cn [Suzhou Institute of Biomedical Engineering and Technology, Chinese Academy of Sciences, Suzhou 215163 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); Tong, Hui; Zhu, Xiaoli [Laboratory of Biosensing Technology, School of Life Sciences, Shanghai University, Shanghai 200444 (China); Liu, Tao; Cheng, Wenbo [Suzhou Institute of Biomedical Engineering and Technology, Chinese Academy of Sciences, Suzhou 215163 (China)

    2014-02-03

    In this report, silver nanoparticles (AgNPs) decorated graphene nanosheets have been prepared based on the reduction of Ag ions by hydroquinone, and their catalytic performance towards the electrochemical oxidation of methanol is investigated. The synthesis of the nano-composite is confirmed by transmission electron microscope measurements and UV-vis absorption spectra. Excellent electrocatalytic performance of the material is demonstrated by cyclic voltammograms. This material also contributes to the low peak potential of methanol oxidation compared with most of the other materials.

  8. Low-Pt-Content Anode Catalyst for Direct Methanol Fuel Cells

    Science.gov (United States)

    Narayanan, Sekharipuram; Whitacre, Jay

    2008-01-01

    Combinatorial experiments have led to the discovery that a nanophase alloy of Pt, Ru, Ni, and Zr is effective as an anode catalyst material for direct methanol fuel cells. This discovery has practical significance in that the electronic current densities achievable by use of this alloy are comparable or larger than those obtained by use of prior Pt/Ru catalyst alloys containing greater amounts of Pt. Heretofore, the high cost of Pt has impeded the commercialization of direct methanol fuel cells. By making it possible to obtain a given level of performance at reduced Pt content (and, hence, lower cost), the discovery may lead to reduction of the economic impediment to commercialization.

  9. Supercritical fluid chromatography coupled with tandem mass spectrometry: A high-efficiency detection technique to quantify Taxane drugs in whole-blood samples.

    Science.gov (United States)

    Jin, Chan; Guan, Jibin; Zhang, Dong; Li, Bing; Liu, Hongzhuo; He, Zhonggui

    2017-10-01

    We present a technique to rapid determine taxane in blood samples by supercritical fluid chromatography together with mass spectrometry. The aim of this study was to develop a supercritical fluid chromatography with mass spectrometry method for the analysis of paclitaxel, cabazitaxel, and docetaxel in whole-blood samples of rats. Liquid-dry matrix spot extraction was selected in sample preparation procedure. Supercritical fluid chromatography separation of paclitaxel, cabazitaxel, docetaxel, and glyburide (internal standard) was accomplished within 3 min by using the gradient mobile phase consisted of methanol as the compensation solvent and carbon dioxide at a flow rate of 1.0 mL/min. The method was validated regarding specificity, the lower limit of quantification, repeatability, and reproducibility of quantification, extraction recovery, and matrix effects. The lower limit of quantification was found to be 10 ng/mL since it exhibited acceptable precision and accuracy at the corresponding level. All interday accuracies and precisions were within the accepted criteria of ±15% of the nominal value and within ±20% at the lower limit of quantification, implying that the method was reliable and reproducible. In conclusion, this method is a promising tool to support and improve preclinical or clinical pharmacokinetic studies with the taxanes anticancer drugs. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Methanol sensor operated in a passive mode

    Science.gov (United States)

    Ren, Xiaoming; Gottesfeld, Shimshon

    2002-01-01

    A sensor outputs a signal related to a concentration of methanol in an aqueous solution adjacent the sensor. A membrane electrode assembly (MEA) is included with an anode side and a cathode side. An anode current collector supports the anode side of the MEA and has a flow channel therethrough for flowing a stream of the aqueous solution and forms a physical barrier to control access of the methanol to the anode side of the MEA. A cathode current collector supports the cathode side of the MEA and is configured for air access to the cathode side of the MEA. A current sensor is connected to measure the current in a short circuit across the sensor electrodes to provide an output signal functionally related to the concentration of methanol in the aqueous solution.

  11. Dynamic signature of molecular association in methanol

    International Nuclear Information System (INIS)

    Bertrand, C. E.; Copley, J. R. D.; Faraone, A.; Self, J. L.

    2016-01-01

    Quasielastic neutron scattering measurements and molecular dynamics simulations were combined to investigate the collective dynamics of deuterated methanol, CD 3 OD. In the experimentally determined dynamic structure factor, a slow, non-Fickian mode was observed in addition to the standard density-fluctuation heat mode. The simulation results indicate that the slow dynamical process originates from the hydrogen bonding of methanol molecules. The qualitative behavior of this mode is similar to the previously observed α-relaxation in supercooled water [M. C. Bellissent-Funel et al., Phys. Rev. Lett. 85, 3644 (2000)] which also originates from the formation and dissolution of hydrogen-bonded associates (supramolecular clusters). In methanol, however, this mode is distinguishable well above the freezing transition. This finding indicates that an emergent slow mode is not unique to supercooled water, but may instead be a general feature of hydrogen-bonding liquids and associating molecular liquids.

  12. Methanol as a cryoprotectant for equine embryos.

    Science.gov (United States)

    Bass, L D; Denniston, D J; Maclellan, L J; McCue, P M; Seidel, G E; Squires, E L

    2004-09-15

    Equine embryos (n=43) were recovered nonsurgically 7-8 days after ovulation and randomly assigned to be cryopreserved in one of two cryoprotectants: 48% (15M) methanol (n=22) or 10% (136 M) glycerol (n=21). Embryos (300-1000 microm) were measured at five intervals after exposure to glycerol (0, 2, 5, 10 and 15 min) or methanol (0, 15, 35, 75 and 10 min) to determine changes (%) in diameter over time (+/-S.D.). Embryos were loaded into 0.25-ml plastic straws, sealed, placed in a programmable cell freezer and cooled from room temperature (22 degrees C) to -6 degrees C. Straws were then seeded, held at -6 degrees C for 10 min and then cooled to -33 degrees C before being plunged into liquid nitrogen. Two or three embryos within a treatment group were thawed and assigned to be either cultured for 12 h prior to transfer or immediately nonsurgically transferred to a single mare. Embryo diameter decreased in all embryos upon initial exposure to cryoprotectant. Embryos in methanol shrank and recovered slightly to 76+/-8 % of their original diameter; however, embryos in glycerol continued to shrink, reaching 57+/-6 % of their original diameter prior to cryopreservation. Survival rates of embryos through Day 16 of pregnancy were 38 and 23%, respectively (P>0.05) for embryos cryopreserved in the presence of glycerol or methanol. There was no difference in pregnancy rates of mares receiving embryos that were cultured prior to transfer or not cultured (P>0.05). Preliminary experiments indicated that 48% methanol was not toxic to fresh equine embryos but methanol provided no advantage over glycerol as a cryoprotectant for equine blastocysts.

  13. Optical coherence tomography findings in methanol toxicity.

    Science.gov (United States)

    Klein, Kendra A; Warren, Alexis K; Baumal, Caroline R; Hedges, Thomas R

    2017-01-01

    Methanol toxicity poses a significant public health problem in developing countries, and in Southeast Asia, where the most common source of poisoning is via adulterated liquor in local drinks. Methanol toxicity can have devastating visual consequences and retinal specialists should be aware of the features of this toxic optic neuropathy. The authors report a case of severe systemic methanol toxicity and relatively mild optic neuropathy demonstrating unique retinal changes on optical coherence tomography (OCT). A previously healthy student developed ataxia, difficulty breathing and loss of consciousness hours after drinking homemade alcohol while traveling in Indonesia. She was found to have a serum pH of 6.79 and elevated methanol levels. She was treated with intravenous ethanol, methylprednisolone and sodium bicarbonate. When she awoke she had bilateral central scotomas. At presentation, she had central depression on visual field testing. OCT of the retinal nerve fiber layer (RNFL) was normal but ganglion cell layer analysis (GCL) showed highly selective loss of the nasal fibers in both eyes. Further, OCT of the macula demonstrated inner nuclear layer (INL) microcysts in the corresponding area of selective GCL loss in both eyes. The selective involvement of the papillomacular bundle fibers is common in toxic optic neuropathies and represents damage to the small caliber axons rich in mitochondria. Despite severe systemic toxicity, the relative sparing of the optic nerve in this case enabled characterization of the evolution of methanol toxicity with segmental GCL involvement and preservation of the RNFL, corresponding to the papillomacular bundle. This is the first reported case of INL microcysts in methanol optic neuropathy and supports that they are a non-specific finding, and may represent preferential damage to the papillomacular bundle.

  14. Photocatalytic conversion of methane to methanol

    Energy Technology Data Exchange (ETDEWEB)

    Taylor, C.E.; Noceti, R.P.; D`Este, J.R. [Pittsburgh Energy Technology Center, PA (United States)

    1995-12-31

    A long-term goal of our research group is the exploration of novel pathways for the direct oxidation of methane to liquid fuels, chemicals, and intermediates. The use of three relatively abundant and inexpensive reactants, light, water, and methane, to produce methanol is attractive. The products of reaction, methanol and hydrogen, are both commercially desirable, methanol being used as is or converted to a variety of other chemicals, and the hydrogen could be utilized in petroleum and/or chemical manufacturing. Methane is produced as a by-product of coal gasification. Depending upon reactor design and operating conditions, up to 18% of total gasifier product may be methane. In addition, there are vast proven reserves of geologic methane in the world. Unfortunately, a large fraction of these reserves are in regions where there is little local demand for methane and it is not economically feasible to transport it to a market. There is a global research effort under way in academia, industry, and government to find methods to convert methane to useful, more readily transportable and storable materials. Methanol, the initial product of methane oxidation, is a desirable product of conversion because it retains much of the original energy of the methane while satisfying transportation and storage requirements. Investigation of direct conversion of methane to transportation fuels has been an ongoing effort at PETC for over 10 years. One of the current areas of research is the conversion of methane to methanol, under mild conditions, using light, water, and a semiconductor photocatalyst. The use of three relatively abundant and inexpensive reactants, light, water, and methane, to produce methanol, is attractive. Research in the laboratory is directed toward applying the techniques developed for the photocatalytic splitting of the water and the photochemical conversion of methane.

  15. Upgrading low-boiling-fraction fast pyrolysis bio-oil using supercritical alcohol: Understanding alcohol participation, chemical composition, and energy efficiency

    International Nuclear Information System (INIS)

    Jo, Heuntae; Prajitno, Hermawan; Zeb, Hassan; Kim, Jaehoon

    2017-01-01

    Highlights: • Non-catalytic and non-hydrogen based bio-oil upgrading was conducted using scMeOH. • 16–40 wt% alcohols were consumed during the upgrading. • High bio-oil yield of 78.4 wt% and low TAN of 4.0 mg KOH/g were achieved. • Effect of supercritical alcohols, reaction times, temperature and bio-oil concentration was conducted. • scMeOH upgrading has good energy recovery (ER) and energy efficiency (EE) compared with scEtOH and scIPA. - Abstract: Herein, a supercritical methanol (scMeOH) route for efficient upgrading of the low-boiling fraction of fast pyrolysis bio-oil containing a large amount of low-molecular-weight acids and water was investigated. The effects of various reaction parameters, including the temperature, concentration, and time, were explored. The yield of bio-oil and the energy efficiency of the scMeOH upgrading process were determined based on the amount of methanol that participated in the reaction during upgrading and fractionation of the upgraded heavy-fraction bio-oils (UHBOs) and upgraded light-fraction bio-oils (ULBOs). Upgrading at 400 °C with 9.1 wt% bio-oil for 30 min generated a high bio-oil yield of 78.4 wt% with a low total acid number (TAN) of 4.0 mg-KOH/g-oil and a higher heating value of 29.9 MJ kg −1 . The energy recovery (ER) was 94–131% and the energy efficiency (EE) was in the range of 79–109% depending on the calorific values of the ULBOs. Compared with upgrading in supercritical ethanol and supercritical isopropanol, less alcohol participation, a lower TAN, and higher ER and EE were achieved with scMeOH upgrading. Plausible pathways for bio-oil upgrading in supercritical alcohols based on detailed compositional analysis of the UHBO, ULBO, and gaseous products were discussed.

  16. Application of response surface methodology for the optimization of supercritical fluid extraction of essential oil from pomegranate (Punica granatum L.) peel.

    Science.gov (United States)

    Ara, Katayoun Mahdavi; Raofie, Farhad

    2016-07-01

    Essential oils and volatile components of pomegranate ( Punica granatum L.) peel of the Malas variety from Meybod, Iran, were extracted using supercritical fluid extraction (SFE) and hydro-distillation methods. The experimental parameters of SFE that is pressure, temperature, extraction time, and modifier (methanol) volume were optimized using a central composite design after a (2 4-1 ) fractional factorial design. Detailed chemical composition of the essential oils and volatile components obtained by hydro-distillation and optimum condition of the supercritical CO 2 extraction were analyzed by GC-MS, and seventy-three and forty-six compounds were identified according to their retention indices and mass spectra, respectively. The optimum SFE conditions were 350 atm pressure, 55 °C temperature, 30 min extraction time, and 150 µL methanol. Results showed that oleic acid, palmitic acid and (-)-Borneol were major compounds in both extracts. The optimum extraction yield was 1.18 % (w/w) for SFE and 0.21 % (v/w) for hydro-distillation.

  17. Grace announces coal-to-methanol project

    Energy Technology Data Exchange (ETDEWEB)

    Myers, R

    1980-02-15

    WR Grace and Co. are planning a feasibility study for a plant to produce 5000 tons/day of methanol and 6000 tons/day of carbon dioxide from captive coal reserves in Colorado. The study will be performed by Energy Transition Co. (ETCo). The producers would be used for pipeline transmission of pulverised coal, probably to California. At the destination the coal would go to a power station, the methanol to a gas turbine and the carbon dioxide to an oil producer for tertiary recovery.

  18. Absolute entropy of ions in methanol

    International Nuclear Information System (INIS)

    Abakshin, V.A.; Kobenin, V.A.; Krestov, G.A.

    1978-01-01

    By measuring the initial thermoelectromotive forces of chains with bromo-silver electrodes in tetraalkylammonium bromide solutions the absolute entropy of bromide-ion in methanol is determined in the 298.15-318.15 K range. The anti Ssub(Brsup(-))sup(0) = 9.8 entropy units value is used for calculation of the absolute partial molar entropy of alkali metal ions and halogenide ions. It has been found that, absolute entropy of Cs + =12.0 entropy units, I - =14.0 entropy units. The obtained ion absolute entropies in methanol at 298.15 K within 1-2 entropy units is in an agreement with published data

  19. Abacavir methanol 2.5-solvate

    Directory of Open Access Journals (Sweden)

    Phuong-Truc T. Pham

    2009-08-01

    Full Text Available The structure of abacavir (systematic name: {(1S,4R-4-[2-amino-6-(cyclopropylamino-9H-purin-9-yl]cyclopent-2-en-1-yl}methanol, C14H18N6O·2.5CH3OH, consists of hydrogen-bonded ribbons which are further held together by additional hydrogen bonds involving the hydroxyl group and two N atoms on an adjacent purine. The asymmetric unit also contains 2.5 molecules of methanol solvate which were grossly disordered and were excluded using SQUEEZE subroutine in PLATON [Spek, (2009. Acta Cryst. D65, 148–155].

  20. Structural Characterisation of Acetogenins from Annona muricata by Supercritical Fluid Chromatography Coupled to High-Resolution Tandem Mass Spectrometry.

    Science.gov (United States)

    Laboureur, Laurent; Bonneau, Natacha; Champy, Pierre; Brunelle, Alain; Touboul, David

    2017-11-01

    Acetogenins are plant polyketides known to be cytotoxic and proposed as antitumor candidates. They are also suspected to be alimentary neurotoxins. Their occurrence as complex mixtures renders their dereplication and structural identification difficult using liquid chromatography coupled to tandem mass spectrometry and efforts are required to improve the methodology. To develop a supercritical fluid chromatography (SFC) high-resolution tandem mass spectrometry method, involving lithium post-column cationisation, for the structural characterisation of Annonaceous acetogenins in crude extracts. The seeds of Annona muricata L. were extracted with methanol. Supercritical fluid chromatography of the extract, using a 2-ethylpyridine stationary phase column, was monitored using a high-resolution quadrupole time-of-flight mass spectrometer. Lithium iodide was added post-column in the make-up solvent. For comparison, the same extract was analysed using high-pressure liquid chromatography coupled to the same mass spectrometer, with a column based on solid core particles. Sensitivity was similar for both HPLC and SFC approaches. Retention behaviour and fragmentation pathways of three different isomer groups are described. A previously unknown group of acetogenins was also evidenced for the first time. The use of SFC-MS/MS allows the reduction of the time of analysis, of environmental impact and an increase in the chromatographic resolution, compared to liquid chromatography. This new methodology enlightened a new group of acetogenins, isomers of montanacin-D. Copyright © 2017 John Wiley & Sons, Ltd. Copyright © 2017 John Wiley & Sons, Ltd.

  1. Magnetohydrodynamically stable plasma with supercritical current density at the axis

    Energy Technology Data Exchange (ETDEWEB)

    Burdakov, A. V. [Budker Institute of Nuclear Physics, 11 Lavrentjev Avenue, 630090 Novosibirsk (Russian Federation); Novosibirsk State Technical University, 20 Karl Marks Avenue, 630092 Novosibirsk (Russian Federation); Postupaev, V. V., E-mail: V.V.Postupaev@inp.nsk.su; Sudnikov, A. V. [Budker Institute of Nuclear Physics, 11 Lavrentjev Avenue, 630090 Novosibirsk (Russian Federation); Novosibirsk State University, 2 Pirogova st., 630090 Novosibirsk (Russian Federation)

    2014-05-15

    In this work, an analysis of magnetic perturbations in the GOL-3 experiment is given. In GOL-3, plasma is collectively heated in a multiple-mirror trap by a high-power electron beam. During the beam injection, the beam-plasma interaction maintains a high-level microturbulence. This provides an unusual radial profile of the net current (that consists of the beam current, current of the preliminary discharge, and the return current). The plasma core carries supercritical current density with the safety factor well below unity, but as a whole, the plasma is stable with q(a) ≈ 4. The net plasma current is counter-directed to the beam current; helicities of the magnetic field in the core and at the edge are of different signs. This forms a system with a strong magnetic shear that stabilizes the plasma core in good confinement regimes. We have found that the most pronounced magnetic perturbation is the well-known n = 1, m = 1 mode for both stable and disruptive regimes.

  2. The Supercritical Pile GRB Model: The Prompt to Afterglow Evolution

    Science.gov (United States)

    Mastichiadis, A.; Kazanas, D.

    2009-01-01

    The "Supercritical Pile" is a very economical GRB model that provides for the efficient conversion of the energy stored in the protons of a Relativistic Blast Wave (RBW) into radiation and at the same time produces - in the prompt GRB phase, even in the absence of any particle acceleration - a spectral peak at energy approx. 1 MeV. We extend this model to include the evolution of the RBW Lorentz factor Gamma and thus follow its spectral and temporal features into the early GRB afterglow stage. One of the novel features of the present treatment is the inclusion of the feedback of the GRB produced radiation on the evolution of Gamma with radius. This feedback and the presence of kinematic and dynamic thresholds in the model can be the sources of rich time evolution which we have began to explore. In particular. one can this may obtain afterglow light curves with steep decays followed by the more conventional flatter afterglow slopes, while at the same time preserving the desirable features of the model, i.e. the well defined relativistic electron source and radiative processes that produce the proper peak in the (nu)F(sub nu), spectra. In this note we present the results of a specific set of parameters of this model with emphasis on the multiwavelength prompt emission and transition to the early afterglow.

  3. Microencapsulation of fish oil using supercritical antisolvent process

    Directory of Open Access Journals (Sweden)

    Fahim Tamzeedul Karim

    2017-07-01

    Full Text Available In order to improve the encapsulation process, a newly supercritical antisolvent process was developed to encapsulate fish oil using hydroxypropyl methyl cellulose as a polymer. Three factors, namely, temperature, pressure, and feed emulsion rate were optimized using response surface methodology. The suitability of the model for predicting the optimum response value was evaluated at the conditions of temperature at 60°C, pressure at 150 bar, and feed rate at 1.36 mL/min. At the optimum conditions, particle size of 58.35 μm was obtained. The surface morphology of the micronized fish oil was also evaluated using field emission scanning electron microscopy where it showed that particles formed spherical structures with no internal voids. Moreover, in vitro release of oil showed that there are significant differences of release percentage of oil between the formulations and the results proved that there was a significant decrease in the in vitro release of oil from the powder when the polymer concentration was high.

  4. Characterization of chromia scales formed in supercritical carbon dioxide

    Energy Technology Data Exchange (ETDEWEB)

    Pint, Bruce A. [ORNL; Unocic, Kinga A. [ORNL; Brese, Robert G. [ORNL; Keiser, James R. [ORNL

    2017-10-01

    Initial experimental work at 700°–800 °C is in progress to develop a lifetime model for supercritical CO2 (sCO2) compatibility for a 30-year lifetime of a >700 °C concentrated solar power system. Nickel-based alloys 282, 740H and 625 and Fe-based alloy 25 are being evaluated in 500-h cycles at 1 and 300 bar, and 10-h cycles in 1 bar industrial grade CO2. The alloys showed similar low rates of oxidation in 1 and 300 bar CO2 in 500-h cycles at 750 °C. However, in 10-h cycles, alloy 25 showed accelerated attack at 700° and 750 °C. Transmission electron microscopy scale cross-sections on alloy 25 after 1000 h at 700 °C in sCO2 and in air only showed a small row of carbides beneath the scale in the former environment. Similar characterisation was performed on alloys 625 and 282 after sCO2 exposure at 750 °C.

  5. Microencapsulation of fish oil using supercritical antisolvent process.

    Science.gov (United States)

    Karim, Fahim Tamzeedul; Ghafoor, Kashif; Ferdosh, Sahena; Al-Juhaimi, Fahad; Ali, Eaqub; Yunus, Kamaruzzaman Bin; Hamed, Mir Hoseini; Islam, Ashraful; Asif, Mohammad; Sarker, Mohammed Zaidul Islam

    2017-07-01

    In order to improve the encapsulation process, a newly supercritical antisolvent process was developed to encapsulate fish oil using hydroxypropyl methyl cellulose as a polymer. Three factors, namely, temperature, pressure, and feed emulsion rate were optimized using response surface methodology. The suitability of the model for predicting the optimum response value was evaluated at the conditions of temperature at 60°C, pressure at 150 bar, and feed rate at 1.36 mL/min. At the optimum conditions, particle size of 58.35 μm was obtained. The surface morphology of the micronized fish oil was also evaluated using field emission scanning electron microscopy where it showed that particles formed spherical structures with no internal voids. Moreover, in vitro release of oil showed that there are significant differences of release percentage of oil between the formulations and the results proved that there was a significant decrease in the in vitro release of oil from the powder when the polymer concentration was high. Copyright © 2017. Published by Elsevier B.V.

  6. METHANOL REMOVAL FROM METHANOL-WATER MIXTURE USING ACTIVATED SLUDGE, AIR STRIPPING AND ADSORPTION PROCESS: COMPARATIVE STUDY

    Directory of Open Access Journals (Sweden)

    SALAM K. AL-DAWERY

    2015-12-01

    Full Text Available An experimental research has been carried out in order to examine the removal of methanol from methanol-water mixtures using three different methods; activated sludge; activated carbon and air stripping. The results showed that the methanol was totally consumed by the bacteria as quickly as the feed entered the activated sludge vessel. Air stripping process has a limited ability for removing of methanol due to strong intermolecular forces between methanol and water; however, the results showed that the percentage of methanol removed using air pressure at 0.5 bar was higher than that of using air pressure of 0.25 bar. Removal of methanol from the mixture with a methanol content of 5% using activated carbon was not successful due to the limited capacity of the of the activated carbon. Thus, the activated sludge process can be considered as the most suitable process for the treatment of methanol-water mixtures.

  7. 37 GHz METHANOL MASERS : HORSEMEN OF THE APOCALYPSE FOR THE CLASS II METHANOL MASER PHASE?

    International Nuclear Information System (INIS)

    Ellingsen, S. P.; Breen, S. L.; Sobolev, A. M.; Voronkov, M. A.; Caswell, J. L.; Lo, N.

    2011-01-01

    We report the results of a search for class II methanol masers at 37.7, 38.3, and 38.5 GHz toward a sample of 70 high-mass star formation regions. We primarily searched toward regions known to show emission either from the 107 GHz class II methanol maser transition, or from the 6.035 GHz excited OH transition. We detected maser emission from 13 sources in the 37.7 GHz transition, eight of these being new detections. We detected maser emission from three sources in the 38 GHz transitions, one of which is a new detection. We find that 37.7 GHz methanol masers are only associated with the most luminous 6.7 and 12.2 GHz methanol maser sources, which in turn are hypothesized to be the oldest class II methanol sources. We suggest that the 37.7 GHz methanol masers are associated with a brief evolutionary phase (of 1000-4000 years) prior to the cessation of class II methanol maser activity in the associated high-mass star formation region.

  8. Sensing methanol concentration in direct methanol fuel cell with total harmonic distortion: Theory and application

    International Nuclear Information System (INIS)

    Mao Qing; Krewer, Ulrike

    2012-01-01

    The nonlinear frequency response of a direct methanol fuel cell (DMFC) is studied by analyzing the total harmonic distortion (THD) spectra. The dependence of the THD spectra on methanol concentration and methanol oxidation kinetics is investigated by means of both simulation and experiment. Simulation using a continuous stirred tank reactor network model suggests that the methanol concentration profile in the anode has a strong impact on the THD spectra. The experimentally observed nonlinear behavior of the DMFC anode can be qualitatively reproduced with a model containing a three-step methanol oxidation mechanism with Kauranen–Frumkin/Temkin kinetics. Both experiment and simulation results show that THD value has a monotonic correlation with methanol concentration at certain frequencies and its sensitivity to concentration is improved with increased current amplitude. The monotonic relationship enables the THD to sense the methanol concentration level by the DMFC itself, which is of mayor interest for the portable application as an external sensor for the system can be omitted.

  9. Sequential Electrodeposition of Platinum-Ruthenium at Boron-Doped Diamond Electrodes for Methanol Oxidation

    Directory of Open Access Journals (Sweden)

    Ileana González-González

    2011-01-01

    Full Text Available Sequential electrodeposition of Pt and Ru on boron-doped diamond (BDD films, in 0.5 M H2SO4 by cyclic voltammetry, has been prepared. The potential cycling, in the aqueous solutions of the respective metals, was between 0.00 and 1.00 V versus Ag/AgCl. The catalyst composites, Pt and PtRu, deposited on BDD film substrates, were tested for methanol oxidation. The modified diamond surfaces were also characterized by scanning electron microscopy-X-ray fluorescence-energy dispersive spectroscopy, X-ray photoelectron spectroscopy, and Auger electron spectroscopy. The scanning Auger electron spectroscopy mapping showed the ruthenium signal only in areas where platinum was electrodeposited. Ruthenium does not deposit on the oxidized diamond surface of the boron-doped diamond. Particles with 5–10% of ruthenium with respect to platinum exhibited better performance for methanol oxidation in terms of methanol oxidation peak current and chronoamperometric current stability. The electrogenerated •OH radicals on BDD may interact with Pt surface, participating in the methanol oxidation as shown in oxidation current and the shift in the peak position. The conductive diamond surface is a good candidate as the support for the platinum electrocatalyst, because it ensures catalytic activity, which compares with the used carbon, and higher stability under severe anodic and cathodic conditions.

  10. Advanced Materials Deposition for Semiconductor Nanostructures Using Supercritical Fluids

    National Research Council Canada - National Science Library

    Wai, Chien M

    2007-01-01

    ... able to dissolve solutes like a liquid and transport dissolved materials like a gas. Metal and metal sulfide nanoparticles of controllable size can be synthesized in supercritical fluid carbon dioxide using water-in-CO2 microemulsion as template...

  11. Destruction of polyphasic systems in supercritical water reaction media

    International Nuclear Information System (INIS)

    Leybros, A.

    2009-12-01

    Spent ion exchange resins (IER) are, hence, radioactive process wastes for which there is no satisfactory industrial treatment. Supercritical water oxidation offers a viable alternative treatment to destroy the organic structure of resins by using supercritical water properties. The reactor used in Supercritical Fluids and Membranes Laboratory is a double shell stirred reactor. Total Organic Carbon reduction rates higher than 99% were obtained thanks to POSCEA2 experimental set-up when using a co-fuel, isopropyl alcohol. Influence of operating parameters was studied. A detailed reactional mechanism for cationic and anionic resins is created. For the solubilization of the particles in supercritical water, a mechanism has been created with the identified rate determining species and implemented into Fluent software through the EDC approach. Experimental temperature profiles are well represented by EDC model. Reaction rates are hence controlled by the chemical species mixing. (author)

  12. Supercritical Water Oxidation Total Organic Carbon (TOC) Analysis

    Science.gov (United States)

    The work presented here is the evaluation of the modified wet‐oxidation method described as Supercritical Water Oxidation (SCWO) for the analysis of total organic carbon (TOC) in very difficult oil/gas produced water sample matrices.

  13. Particle Formation by Supercritical Fluid Extraction and Expansion Process

    Directory of Open Access Journals (Sweden)

    Sujuan Pan

    2013-01-01

    Full Text Available Supercritical fluid extraction and expansion (SFEE patented technology combines the advantages of both supercritical fluid extraction (SFE and rapid expansion of supercritical solution (RESS with on-line coupling, which makes the nanoparticle formation feasible directly from matrix such as Chinese herbal medicine. Supercritical fluid extraction is a green separation technology, which has been developed for decades and widely applied in traditional Chinese medicines or natural active components. In this paper, a SFEE patented instrument was firstly built up and controlled by LABVIEW work stations. Stearic acid was used to verify the SFEE process at optimized condition; via adjusting the preexpansion pressure and temperature one can get different sizes of particles. Furthermore, stearic acid was purified during the SFEE process with HPLC-ELSD detecting device; purity of stearic acid increased by 19%, and the device can purify stearic acid.

  14. Supercritical Fluid Extraction of Seed Oil from Chinese Licorice ...

    African Journals Online (AJOL)

    NJD

    2005-12-17

    Dec 17, 2005 ... a Key Laboratory of Forest Plant Ecology, Northeast Forestry University, Hexing Road 26, 150040, ... Carbon dioxide, the most commonly used supercritical fluid, has ... absorb the remaining water that the chloroform layer had.

  15. Plasticisation and complexation of certain polymers in supercritical CO2

    CSIR Research Space (South Africa)

    Labuschagne, Philip W

    2004-09-01

    Full Text Available A polymer system (polyvinylpyrrolidone + polyvinyl acetate-co-crotonic acid) was successfully identified for use as encapsulation material for sensitive actives using supercritical CO2 as plasticisation medium, having the following properties: 1...

  16. Supercritical fluid technology for energy and environmental applications

    CERN Document Server

    Anikeev, Vladimir

    2014-01-01

    Supercritical Fluid Technology for Energy and Environmental Applications covers the fundamental principles involved in the preparation and characterization of supercritical fluids (SCFs) used in the energy production and other environmental applications. Energy production from diversified resources - including renewable materials - using clean processes can be accomplished using technologies like SCFs. This book is focused on critical issues scientists and engineers face in applying SCFs to energy production and environmental protection, the innovative solutions they have found, and the challenges they need to overcome. The book also covers the basics of sub- and supercritical fluids, like the thermodynamics of phase and chemical equilibria, mathematical modeling, and process calculations. A supercritical fluid is any substance at a temperature and pressure above its critical point where distinct liquid and gas phases do not exist. At this state the compound demonstrates unique properties, which can be "fine...

  17. Adsorption of methanol molecule on graphene: Experimental results and first-principles calculations

    Science.gov (United States)

    Zhao, X. W.; Tian, Y. L.; Yue, W. W.; Chen, M. N.; Hu, G. C.; Ren, J. F.; Yuan, X. B.

    2018-04-01

    Adsorption properties of methanol molecule on graphene surface are studied both theoretically and experimentally. The adsorption geometrical structures, adsorption energies, band structures, density of states and the effective masses are obtained by means of first-principles calculations. It is found that the electronic characteristics and conductivity of graphene are sensitive to the methanol molecule adsorption. After adsorption of methanol molecule, bandgap appears. With the increasing of the adsorption distance, the bandgap, adsorption energy and effective mass of the adsorption system decreased, hence the resistivity of the system decreases gradually, these results are consistent with the experimental results. All these calculations and experiments indicate that the graphene-based sensors have a wide range of applications in detecting particular molecules.

  18. Supercritical Regeneration of an Activated Carbon Fiber Exhausted with Phenol

    OpenAIRE

    M. Jesus Sanchez-Montero; Jennifer Pelaz; Nicolas Martin-Sanchez; Carmen Izquierdo; Francisco Salvador

    2018-01-01

    The properties of supercritical CO2 (SCCO2) and supercritical water (SCW) turn them into fluids with a great ability to remove organic adsorbates retained on solids. These properties were used herein to regenerate an activated carbon fiber (ACF) saturated with a pollutant usually contained in wastewater and drinking water, phenol. Severe regeneration conditions, up to 225 bar and 400 °C, had to be employed in SCCO2 regeneration to break the strong interaction established between phenol and th...

  19. Thermodynamic analysis and numerical modeling of supercritical injection

    OpenAIRE

    Banuti, Daniel

    2015-01-01

    Although liquid propellant rocket engines are operational and have been studied for decades, cryogenic injection at supercritical pressures is still considered essentially not understood. This thesis intends to approach this problem in three steps: by developing a numerical model for real gas thermodynamics, by extending the present thermodynamic view of supercritical injection, and finally by applying these methods to the analysis of injection. A new numerical real gas thermodynamics mode...

  20. Carbon-Supported Pd and PdFe Alloy Catalysts for Direct Methanol Fuel Cell Cathodes

    Directory of Open Access Journals (Sweden)

    Luis M. Rivera Gavidia

    2017-05-01

    Full Text Available Direct methanol fuel cells (DMFCs are electrochemical devices that efficiently produce electricity and are characterized by a large flexibility for portable applications and high energy density. Methanol crossover is one of the main obstacles for DMFC commercialization, forcing the search for highly electro-active and methanol tolerant cathodes. In the present work, carbon-supported Pd and PdFe catalysts were synthesized using a sodium borohydride reduction method and physico-chemically characterized using transmission electron microscopy (TEM and X-ray techniques such as photoelectron spectroscopy (XPS, diffraction (XRD and energy dispersive spectroscopy (EDX. The catalysts were investigated as DMFC cathodes operating at different methanol concentrations (up to 10 M and temperatures (60 °C and 90 °C. The cell based on PdFe/C cathode presented the best performance, achieving a maximum power density of 37.5 mW·cm−2 at 90 °C with 10 M methanol, higher than supported Pd and Pt commercial catalysts, demonstrating that Fe addition yields structural changes to Pd crystal lattice that reduce the crossover effects in DMFC operation.

  1. Methanol electro-oxidation on Pt/C modified by polyaniline nanofibers for DMFC applications

    Energy Technology Data Exchange (ETDEWEB)

    Zhiani, Mohammad; Rezaei, Behzad; Jalili, Jalal [Department of Chemistry, Isfahan University of Technology, Isfahan 84156-83111 (Iran)

    2010-09-15

    In the present study, in order to achieve an inexpensive tolerable anode catalyst for direct methanol fuel cell applications, a composite of polyaniline nanofibers and Pt/C nano-particles, identified by PANI/Pt/C, was prepared by in-situ electropolymerization of aniline and trifluoromethane sulfonic acid on glassy carbon. The effect of synthesized PANI nanofibers in methanol electrooxidation reaction was compared by bare Pt/C by different electrochemical methods such as; cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and chronoamperometry. Scanning electron microscopy (SEM) was also employed to morphological study of the modified catalyst layer. The test results reveal that introduction of PANI nanofibers within catalyst layer improves the catalyst activity in methanol oxidation, hinders and prevents catalyst from more poisoning by intermediate products of methanol oxidation and improves the mechanical properties of the catalyst layer. SEM images also indicate that PANI nanofibers placed between platinum particles and anchor platinum particles and alleviate the Pt migration during methanol electrooxidation. (author)

  2. Electro-oxidation of methanol diffused through proton exchange membrane on Pt surface: crossover rate of methanol

    International Nuclear Information System (INIS)

    Jung, Inhwa; Kim, Doyeon; Yun, Yongsik; Chung, Suengyoung; Lee, Jaeyoung; Tak, Yongsug

    2004-01-01

    Methanol crossover rate through proton exchange membrane (Nafion 117) was investigated with a newly designed electrochemical stripping cell. Nanosize Pt electrode was prepared by the electroless deposition. Distinct electrocatalytic oxidation behaviors of methanol inside membrane were similar to the methanol oxidation in aqueous electrolyte, except adsorption/desorption of hydrogen. The amount of methanol diffused through membrane was calculated from the charge of methanol oxidation during repetitive cyclic voltammetry (CV) and methanol crossover rate was estimated to be 0.69 nmol/s

  3. Supercritical carbon dioxide for textile applications and recent developments

    Science.gov (United States)

    Eren, H. A.; Avinc, O.; Eren, S.

    2017-10-01

    In textile industry, supercritical carbon dioxide (scCO2), possessing liquid-like densities, mostly find an application on textile dyeing processes such as providing hydrophobic dyes an advantage on dissolving. Their gas-like low viscosities and diffusion properties can result in shorter dyeing periods in comparison with the conventional water dyeing process. Supercritical carbon dioxide dyeing is an anhydrous dyeing and this process comprises the usage of less energy and chemicals when compared to conventional water dyeing processes leading to a potential of up to 50% lower operation costs. The advantages of supercritical carbon dioxide dyeing method especially on synthetic fiber fabrics hearten leading textile companies to alter their dyeing method to this privileged waterless dyeing technology. Supercritical carbon dioxide (scCO2) waterless dyeing is widely known and applied green method for sustainable and eco-friendly textile industry. However, not only the dyeing but also scouring, desizing and different finishing applications take the advantage of supercritical carbon dioxide (scCO2). In this review, not only the principle, advantages and disadvantages of dyeing in supercritical carbon dioxide but also recent developments of scCO2 usage in different textile processing steps such as scouring, desizing and finishing are explained and commercial developments are stated and summed up.

  4. Effects of Gravity on Supercritical Water Oxidation (SCWO) Processes

    Science.gov (United States)

    Hegde, Uday; Hicks, Michael

    2013-01-01

    The effects of gravity on the fluid mechanics of supercritical water jets are being studied at NASA to develop a better understanding of flow behaviors for purposes of advancing supercritical water oxidation (SCWO) technologies for applications in reduced gravity environments. These studies provide guidance for the development of future SCWO experiments in new experimental platforms that will extend the current operational range of the DECLIC (Device for the Study of Critical Liquids and Crystallization) Facility on board the International Space Station (ISS). The hydrodynamics of supercritical fluid jets is one of the basic unit processes of a SCWO reactor. These hydrodynamics are often complicated by significant changes in the thermo-physical properties that govern flow behavior (e.g., viscosity, thermal conductivity, specific heat, compressibility, etc), particularly when fluids transition from sub-critical to supercritical conditions. Experiments were conducted in a 150 ml reactor cell under constant pressure with water injections at various flow rates. Flow configurations included supercritical jets injected into either sub-critical or supercritical water. Profound gravitational influences were observed, particularly in the transition to turbulence, for the flow conditions under study. These results will be presented and the parameters of the flow that control jet behavior will be examined and discussed.

  5. Supercritical extraction of lycopene from tomato industrial wastes with ethane.

    Science.gov (United States)

    Nobre, Beatriz P; Gouveia, Luisa; Matos, Patricia G S; Cristino, Ana F; Palavra, António F; Mendes, Rui L

    2012-07-11

    Supercritical fluid extraction of all-E-lycopene from tomato industrial wastes (mixture of skins and seeds) was carried out in a semi-continuous flow apparatus using ethane as supercritical solvent. The effect of pressure, temperature, feed particle size, solvent superficial velocity and matrix initial composition was evaluated. Moreover, the yield of the extraction was compared with that obtained with other supercritical solvents (supercritical CO₂ and a near critical mixture of ethane and propane). The recovery of all-E-lycopene increased with pressure, decreased with the increase of the particle size in the initial stages of the extraction and was not practically affected by the solvent superficial velocity. The effect of the temperature was more complex. When the temperature increased from 40 to 60 °C the recovery of all-E-lycopene increased from 80 to 90%. However, for a further increase to 80 °C, the recovery remained almost the same, indicating that some E-Z isomerization could have occurred, as well as some degradation of lycopene. The recovery of all-E-lycopene was almost the same for feed samples with different all-E-lycopene content. Furthermore, when a batch with a higher all-E-lycopene content was used, supercritical ethane and a near critical mixture of ethane and propane showed to be better solvents than supercritical CO₂ leading to a faster extraction with a higher recovery of the carotenoid.

  6. Hydrogenation of diesel aromatic compounds in supercritical solvent environment

    Directory of Open Access Journals (Sweden)

    E.P. Martins

    2000-09-01

    Full Text Available Reactions under supercritical conditions have been employed in many processes. Furthermore, an increasing number of commercial reactions have been conducted under supercritical or near critical conditions. These reaction conditions offer several advantages when compared to conditions in conventional catalytic processes in liquid-phase, gas-liquid interface, or even some gas-phase reactions. Basically, a supercritical solvent can diminish the reactant’s transport resistance from the bulk region to the catalyst surface due to enhancement of liquid diffusivity values and better solubility than those in different phases. Another advantage is that supercritical solvents permit prompt and easy changes in intermolecular properties in order to modify reaction parameters, such as conversion or selectivity, or even proceed with the separation of reaction products. Diesel fractions from petroleum frequently have larger than desirable quantities of aromatic compounds. Diesel hydrogenation is intended to decrease these quantities, i.e., to increase the quantity of paraffin present in this petroleum fraction. In this work, the hydrogenation of tetralin was studied as a model reaction for the aromatic hydrogenation process. A conventional gas-liquid-solid catalytic process was compared with that of supercritical carbon dioxide substrate under similar conditions. Additionally, an equilibrium conversion diagram was calculated for this reaction in a wide range of temperature and reactant ratios, so as to optimize the operational conditions and improve the results of subsequent experiments. An increase in the rate of reaction at 493 K in supercritical fluid, as compared to that in the conventional process, was observed.

  7. High Materials Performance in Supercritical CO2 in Comparison with Atmospheric Pressure CO2 and Supercritical Steam

    Energy Technology Data Exchange (ETDEWEB)

    Holcomb, Gordon [National Energy Technology Lab. (NETL), Pittsburgh, PA, (United States); Tylczak, Joseph [National Energy Technology Lab. (NETL), Pittsburgh, PA, (United States); Carney, Casey [National Energy Technology Lab. (NETL), Pittsburgh, PA, (United States); Dogan, Omer N. [National Energy Technology Lab. (NETL), Pittsburgh, PA, (United States)

    2017-02-26

    This presentation covers environments (including advanced ultra-supercritical (A-USC) steam boiler/turbine and sCO2 indirect power cycle), effects of pressure, exposure tests, oxidation results, and mechanical behavior after exposure.

  8. Heat transfer study under supercritical pressure conditions

    International Nuclear Information System (INIS)

    Yamashita, Tohru; Yoshida, Suguru; Mori, Hideo; Morooka, Shinichi; Komita, Hideo; Nishida, Kouji

    2003-01-01

    Experiments were performed on heat transfer and pressure drop of a supercritical pressure fluid flowing upward in a uniformly heated vertical tube of a small diameter, using HCFC22 as a test fluid. Following results were obtained. (1) Characteristics of the heat transfer are similar to those for the tubes of large diameter. (2) The effect of tube diameter on the heat transfer was seen for a 'normal heat transfer, but not for a 'deteriorated' heat transfer. (3) The limit heat flux for the occurrence of deterioration in heat transfer becomes larger with smaller diameter tube. (4) The Watts and Chou correlation has the best prediction performance for the present data in the 'normal' heat transfer region. (5) Frictional pressure drop becomes smaller than that for an isothermal flow in the region near the pseudocritical point, and this reduction was more remarkable for the deteriorated' heat transfer. (author)

  9. Development of ultra supercritical (USC) power plant

    Energy Technology Data Exchange (ETDEWEB)

    Chang, Sung Ho; Kim, Bum Soo [KEPCO Research Institute, Daejeon (Korea, Republic of); Min, Taek Ki [Chung Nat' l Univ., Cheongwon (Korea, Republic of)

    2012-02-15

    For environmental reasons and because of our limited energy resources, high efficiency power generation technology will be necessary in the future. Ultra supercritical (USC) power generation technology is the key to managing the greenhouse gas problems and energy resource problems discussed in the Kyoto Protocol to the United Nations Framework Convention on Climate Change. Other countries and manufacturers are trying to build commercial power plants. In this paper, an efficient method of achieving near zero emission operation of a high efficiency fossil power plant using USC power generation is discussed. Development of USC power generation in Korea has been supported by the Korean government in two phases: Phase I was USC key technology development from 2002 to 2008, and Phase II is USC development and technology optimization from 2010 to 2017.

  10. Instrumentation for analytical scale supercritical fluid chromatography.

    Science.gov (United States)

    Berger, Terry A

    2015-11-20

    Analytical scale supercritical fluid chromatography (SFC) is largely a sub-discipline of high performance liquid chromatography (HPLC), in that most of the hardware and software can be used for either technique. The aspects that separate the 2 techniques stem from the use of carbon dioxide (CO2) as the main component of the mobile phase in SFC. The high compressibility and low viscosity of CO2 mean that pumps, and autosamplers designed for HPLC either need to be modified or an alternate means of dealing with compressibility needs to be found. The inclusion of a back pressure regulator and a high pressure flow cell for any UV-Vis detector are also necessary. Details of the various approaches, problems and solutions are described. Characteristics, such as adiabatic vs. isothermal compressibility, thermal gradients, and refractive index issues are dealt with in detail. Copyright © 2015 Elsevier B.V. All rights reserved.

  11. Pentagonal dodecahedron methane hydrate cage and methanol ...

    Indian Academy of Sciences (India)

    methane hydrate in sea bed near continental margin and underneath of permafrost ... clathrate structure,6,7 IR spectroscopy analysis of vibra- tional form of guest .... Hydrogen (H71) of the hydroxyl group of methanol is found to have formed ...

  12. Parameters affecting methanol utilization by yeasts

    Energy Technology Data Exchange (ETDEWEB)

    Foda, M.S.; El-Masry, H.G.

    1981-01-01

    Screening of 28 yeast cultures, representing 22 species of various yeasts, with respect to their capabilities to assimilate methanol, has shown that this property was mostly found in certain species of the two genera Hansenula and Candida. When methanol was used as a sole carbon source for a methanol-adapted strain of Hansenula polymorpha, a linear yield response could be obtained with increasing alcohol up to 2% concentration. The amount of inoculum proved to be the decisive factor in determining a priori the ability of the organism to grow at 6% methanol as final concentration. The optimum pH values for growth ranged between 4.5-5.5 with no growth at pH 6.5 or higher. A marked growth stimulation was obtained when the medium was supplied with phosphate up to 0.08 M as final concentration. Within the nitrogen sources tested, corn steep liquor concentrate gave the highest yield of cells. The significance of the obtained results are discussed with reference to feasibilities of application.

  13. Metacridamide B methanol-d4 monosolvate

    Science.gov (United States)

    The title compound was extracted from conidia of the fungus Metarhizium acridum. Crystals were obtained as a methanol-d4 solvate. The tail part of the 4-methylhexan-2-yl group exhibits disorder over two positions, with an occupancy ratio of 0.682 (9):0.318 (9). The crystal structure confirms the abs...

  14. Methanol fractionations of Catha edulis frosk (Celastraceae ...

    African Journals Online (AJOL)

    The study investigated the effect of methanol extract and its fractionations obtained from Yemeni khat on the smooth muscle isometric tension in Lewis rat aortal ring preparations and compared the effects of the crimson and green leaves. Khat leaves were sorted into green (khat Light; KL) and crimson (khat Dark; KD) leaves ...

  15. Methanex, Hoechst Celanese dissolve methanol partnership

    International Nuclear Information System (INIS)

    Morris, G.D.L.

    1993-01-01

    One of the many joint venture alliances recently announced in the petrochemical sector is ending in divorce. Hoechst Celanese Chemical (Dallas) and Methanex Corp. (Vancouver) are in the process of dissolving the partnership they had formed to restart Hoechst Celanese's methanol plant at Clear Lake, TX. Hoechst Celanese says it is actively seeking replacement partners and has several likely prospects, while Methanex is concentrating on its other ventures. Those include its just-completed acquisition of Fletcher Challenge's (Auckland, NZ) methanol business and a joint venture with American Cyanamid to convert an ammonia plant at Fortier, LA to methanol. Methanex will still be the world's largest producer of methanol. Officially, the negotiations between Methanex and Hoechst Celanese 'just broke down over the last month or so,' says Steve Yurich, operations manager for the Clear Lake plant. Market sources, however, say that Methanex found itself 'with too many irons in the fire' and pulled out before it ran into financial or perhaps even antitrust difficulties

  16. Conversion of methanol and isobutanol to MTBE

    CSIR Research Space (South Africa)

    Nicolaides, CP

    1993-09-24

    Full Text Available Over the resin catalyst Amberlyst 15, and under our reaction conditions, the yield of MTBE (methyl tert-butyl ether), from the reaction of methanol and isobutene, is at a maximum in the temperature rang of 40-60-degrees-C. Slightly higher...

  17. Comparative antitrypanosomal screening of methanolic extracts of ...

    African Journals Online (AJOL)

    The in vitro and in vivo activities of methanolic extracts of defatted leaves and stems of Khaya senegalensis and Moringa oleifera on Trypanosoma brucei brucei were investigated and compared. The in vitro assessment involved incubating the parasite (in triplicate) in the presence of various extract concentrations in a ...

  18. Cancer chemopreventive property of Bidens pilosa methanolic ...

    African Journals Online (AJOL)

    Cancer chemopreventive property of Bidens pilosa methanolic extract on two stage in vivo skin carcinogenesis model. ... In the forestomach, kidney and lung, glutathione S-transferase and DT-diaphorase levels were significantly reduced. Chemopreventive response was calculated by the mean number of papillomas ...

  19. Numerical modelling of methanol liquid pool fires

    Science.gov (United States)

    Prasad, Kuldeep; Li, Chiping; Kailasanath, K.; Ndubizu, Chuka; Ananth, Ramagopal; Tatem, P. A.

    1999-12-01

    The focus of this paper is on numerical modelling of methanol liquid pool fires. A mathematical model is first developed to describe the evaporation and burning of a two-dimensional or axisymmetric pool containing pure liquid methanol. Then, the complete set of unsteady, compressible Navier-Stokes equations for reactive flows are solved in the gas phase to describe the convection of the fuel gases away from the pool surface, diffusion of the gases into the surrounding air and the oxidation of the fuel into product species. Heat transfer into the liquid pool and the metal container through conduction, convection and radiation are modelled by solving a modified form of the energy equation. Clausius-Clapeyron relationships are invoked to model the evaporation rate of a two-dimensional pool of pure liquid methanol. The governing equations along with appropriate boundary and interface conditions are solved using the flux-corrected transport algorithm. Numerical results exhibit a flame structure that compares well with experimental observations. Temperature profiles and burning rates were found to compare favourably with experimental data from single- and three-compartment laboratory burners. The model predicts a puffing frequency of approximately 12 Hz for a 1 cm diameter methanol pool in the absence of any air co-flow. It is also observed that increasing the air co-flow velocity helps in stabilizing the diffusion flame, by pushing the vortical structures away from the flame region.

  20. Preliminary antidiarrhoeal activity of methanolic extracts of ...

    African Journals Online (AJOL)

    Securinega virosa is used as remedy for diarrhoea in tropical Africa, but has not been investigated for its antidiarrhoeal activity. This study was therefore aimed at investigating the methanolic extracts of the leaves, stem bark and root bark for antidirrhoeal activity, using castor oil-induced diarrhoeal model in mice. The effects ...

  1. Antifungal evaluation and phytochemical screening of methanolic ...

    African Journals Online (AJOL)

    The objective of the study was to further examine the medicinal value of Boswellia dalzielii plant by evaluating the antifungal activity and carrying out phytochemical screening of methanolic extract, hexane, ethyl acetate, aqueous fractions and the sub-fractions of the stem bark of the plant. Standard methods were used for ...

  2. Effect of Ni Core Structure on the Electrocatalytic Activity of Pt-Ni/C in Methanol Oxidation

    Directory of Open Access Journals (Sweden)

    Vladimir Linkov

    2013-07-01

    Full Text Available Methanol oxidation catalysts comprising an outer Pt-shell with an inner Ni-core supported on carbon, (Pt-Ni/C, were prepared with either crystalline or amorphous Ni core structures. Structural comparisons of the two forms of catalyst were made using transmission electron microscopy (TEM, X-ray diffraction (XRD and X-ray photoelectron spectroscopy (XPS, and methanol oxidation activity compared using CV and chronoamperometry (CA. While both the amorphous Ni core and crystalline Ni core structures were covered by similar Pt shell thickness and structure, the Pt-Ni(amorphous/C catalyst had higher methanol oxidation activity. The amorphous Ni core thus offers improved Pt usage efficiency in direct methanol fuel cells.

  3. On-line methanol sensor system development for recombinant ...

    African Journals Online (AJOL)

    On-line methanol sensor system development for recombinant human serum ... of the methanol sensor system was done in a medium environment with yeast cells ... induction at a low temperature and a pH where protease does not function.

  4. Evaluation of the Ramazzini Foundation Study of Methanol in Rats

    Science.gov (United States)

    Evaluation of the Ramazzini Foundation Study of Methanol in Rats: A Comparison of Diagnoses by the RF Study Pathologist and a Recent NTP Review Team, summarized by George Cruzan and submitted to the Methanol Institute

  5. In vitro evaluation of the interaction between methanol extract of ...

    African Journals Online (AJOL)

    Antimicrobial interaction studies between methanol extract of lichen (Ramalina farinacea (I) ach. (Fam: Ramalinacea) and tetracycline, against clinical isolates of Staphylococcus aureus was evaluated. Preliminary antimicrobial properties of the extract were evaluated. Antimicrobial interaction studies between the methanol ...

  6. The possible mechanisms for the antifertility action of methanolic ...

    African Journals Online (AJOL)

    The possible mechanisms for the antifertility action of methanolic root extract of Rumex steudelii. ... African Health Sciences ... Objectives: The present study focused further on the possible mechanisms of the antifertility effect of the methanolic ...

  7. Observation of carbon growth and interface structures in methanol solution

    Science.gov (United States)

    Okuno, Kimio

    2015-11-01

    In the deposition of carbon on the surface of a tungsten tip in methanol solution by electrolysis, the growth structure of the carbon films, the interface state, and the dissolution of carbon atoms into the tungsten matrix of the substrate have been investigated with the atomic events by field ion microscopy (FIM). The carbon films preferentially condense on the W{111} plane. The interfacial reaction at the carbon atom-tungsten substrate interface is vigorous and the carbon atoms also readily dissolve into the substrate matrix to form a tungsten-carbon complex. The reaction depth of the deposited carbon depends on the magnitude of electrolytic current and the treatment duration in the methanol solution. In this work, the resolution depth of carbon was found to be approximately 270 atomic layers below the top layer of the tungsten substrate by a field evaporation technique. In the case of a low electrolytic current, the tungsten substrate surface is entirely covered with carbon atoms having a pseudomorphic structure. The field-electron emission characteristics were also evaluated for various coverages of the carbon film formed on the substrate.

  8. Assessment of hydrogen bonding effect on ionization of water from ambient to supercritical region–MD simulation approach

    International Nuclear Information System (INIS)

    Swiatla-Wojcik, D.; Mozumder, A.

    2014-01-01

    We present a novel, molecular dynamics (MD) simulation based, strategy to analyze how the degree of hydrogen bonding may influence the ionization and dissociation of water upon heating from ambient to supercritical temperatures. Calculations show a negligible change in the ionization energy up to 200 °C. At higher temperatures the ionization energy increases due to the decreasing degree of hydrogen bonding. The influence of density (pressure) is pronounced in the supercritical region. The ionization is more energy consuming in the less dense fluid. We also show that high temperature and low density may promote dissociation of the electronically excited water molecules. Implications on the initial radiation chemical yields of the hydrated electron, hydrogen atom and hydroxyl radical are discussed. - Highlights: • Up to 200 °C changes in the vertical and adiabatic ionization potentials are negligible. • At higher temperatures ionization is more energy consuming. • Ionization potential increases with decreasing density of supercritical water. • High temperature and low density promote dissociation of the excited molecules

  9. Effect of methanol ratio in mixed solvents on optical properties and wettability of ZnO films by cathodic electrodeposition

    International Nuclear Information System (INIS)

    Zhang, Miao; Xu, Kai; Jiang, Xishun; Yang, Lei; He, Gang; Song, Xueping; Sun, Zhaoqi; Lv, Jianguo

    2014-01-01

    Highlights: • Different surface morphologies of ZnO films were prepared by cathodic electrodeposition. • The surface morphologies are controlled through add different ratio methanol to electrolyte. • The morphology changes from nanorods with hexagonal structure to net-like nanostructure. • The wettability of films shows obvious change with increasing methanol ratio. • The maximum light-induced CA change has been observed with the methanol ratio of 0.8. - Abstract: ZnO thin films were prepared in the electrolyte with different methanol ratio by cathodic electrodeposition method. Microstructure, surface morphology, optical properties and wettability of the thin films were investigated by X-ray diffractometer, field-emission scanning electron microscope, ultraviolet–visible spectroscope, fluorescence spectrometer and water contact angle apparatus. Increase of methanol ratio in the solvents may restrain the (0 0 2) plane preferential orientation in some extent. Change of current density curves with the ratio of methanol in the solution play a vital role on electrochemical reaction kinetics, microstructure and/or surface morphology of ZnO thin films. With the methanol ratio increase from 0 to 0.8, the surface morphology changes from nanorods to net-like nanostructure. The adsorbed NO 3 − ions on the polar planes hinder the crystal growth along the c-axis and redirect the growth direction along the nonpolar planes. The maximum and minimum band gaps have been obtained in the ZnO thin films with the methanol ratio of 0.4 and 0.6, respectively. Change of contact angle before UV irradiation may be related to surface morphology and oxygen vacancies. The maximum light-induced water contact angle change has been observed in the sample with the methanol ratio of 0.8. The results may be attributed to the higher surface roughness and net-like morphology

  10. Effect of methanol ratio in mixed solvents on optical properties and wettability of ZnO films by cathodic electrodeposition

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Miao; Xu, Kai; Jiang, Xishun; Yang, Lei; He, Gang; Song, Xueping [School of Physics and Material Science, Anhui University, Hefei 230601 (China); Sun, Zhaoqi, E-mail: szq@ahu.edu.cn [School of Physics and Material Science, Anhui University, Hefei 230601 (China); Lv, Jianguo, E-mail: lvjg1@163.com [School of Electronic and Information Engineering, Hefei Normal University, Hefei 230601 (China)

    2014-12-05

    Highlights: • Different surface morphologies of ZnO films were prepared by cathodic electrodeposition. • The surface morphologies are controlled through add different ratio methanol to electrolyte. • The morphology changes from nanorods with hexagonal structure to net-like nanostructure. • The wettability of films shows obvious change with increasing methanol ratio. • The maximum light-induced CA change has been observed with the methanol ratio of 0.8. - Abstract: ZnO thin films were prepared in the electrolyte with different methanol ratio by cathodic electrodeposition method. Microstructure, surface morphology, optical properties and wettability of the thin films were investigated by X-ray diffractometer, field-emission scanning electron microscope, ultraviolet–visible spectroscope, fluorescence spectrometer and water contact angle apparatus. Increase of methanol ratio in the solvents may restrain the (0 0 2) plane preferential orientation in some extent. Change of current density curves with the ratio of methanol in the solution play a vital role on electrochemical reaction kinetics, microstructure and/or surface morphology of ZnO thin films. With the methanol ratio increase from 0 to 0.8, the surface morphology changes from nanorods to net-like nanostructure. The adsorbed NO{sub 3}{sup −} ions on the polar planes hinder the crystal growth along the c-axis and redirect the growth direction along the nonpolar planes. The maximum and minimum band gaps have been obtained in the ZnO thin films with the methanol ratio of 0.4 and 0.6, respectively. Change of contact angle before UV irradiation may be related to surface morphology and oxygen vacancies. The maximum light-induced water contact angle change has been observed in the sample with the methanol ratio of 0.8. The results may be attributed to the higher surface roughness and net-like morphology.

  11. Selectivity of Direct Methanol Fuel Cell Membranes

    Directory of Open Access Journals (Sweden)

    Antonino S. Aricò

    2015-11-01

    Full Text Available Sulfonic acid-functionalized polymer electrolyte membranes alternative to Nafion® were developed. These were hydrocarbon systems, such as blend sulfonated polyetheretherketone (s-PEEK, new generation perfluorosulfonic acid (PFSA systems, and composite zirconium phosphate–PFSA polymers. The membranes varied in terms of composition, equivalent weight, thickness, and filler and were investigated with regard to their methanol permeation characteristics and proton conductivity for application in direct methanol fuel cells. The behavior of the membrane electrode assemblies (MEA was investigated in fuel cell with the aim to individuate a correlation between membrane characteristics and their performance in a direct methanol fuel cell (DMFC. The power density of the DMFC at 60 °C increased according to a square root-like function of the membrane selectivity. This was defined as the reciprocal of the product between area specific resistance and crossover. The power density achieved at 60 °C for the most promising s-PEEK-based membrane-electrode assembly (MEA was higher than the benchmark Nafion® 115-based MEA (77 mW·cm−2 vs. 64 mW·cm−2. This result was due to a lower methanol crossover (47 mA·cm−2 equivalent current density for s-PEEK vs. 120 mA·cm−2 for Nafion® 115 at 60 °C as recorded at OCV with 2 M methanol and a suitable area specific resistance (0.15 Ohm cm2 for s-PEEK vs. 0.22 Ohm cm2 for Nafion® 115.

  12. Erythropoietin in Treatment of Methanol Optic Neuropathy.

    Science.gov (United States)

    Pakdel, Farzad; Sanjari, Mostafa S; Naderi, Asieh; Pirmarzdashti, Niloofar; Haghighi, Anousheh; Kashkouli, Mohsen B

    2018-06-01

    Methanol poisoning can cause an optic neuropathy that is usually severe and irreversible and often occurs after ingestion of illicit or homemade alcoholic beverages. In this study, we evaluated the potential neuroprotective effect of erythropoietin (EPO) on visual acuity (VA) in patients with methanol optic neuropathy. In a prospective, noncomparative interventional case series, consecutive patients with methanol optic neuropathy after alcoholic beverage ingestion were included. All patients initially received systemic therapy including metabolic stabilization and detoxification. Treatment with intravenous recombinant human EPO consisted of 20,000 units/day for 3 successive days. Depending on clinical response, some patients received a second course of EPO. VA, funduscopy, and spectral domain optical coherence tomography were assessed during the study. Main outcome measure was VA. Thirty-two eyes of 16 patients with methanol optic neuropathy were included. Mean age was 34.2 years (±13.3 years). The mean time interval between methanol ingestion and treatment with intravenous EPO was 9.1 days (±5.56 days). Mean follow-up after treatment was 7.5 months (±5.88 months). Median VA in the better eye of each patient before treatment was light perception (range: 3.90-0.60 logMAR). Median last acuity after treatment in the best eye was 1.00 logMAR (range: 3.90-0.00 logMAR). VA significantly increased in the last follow-up examination (P optic neuropathy and may represent a promising treatment for this disorder.

  13. Selectivity of Direct Methanol Fuel Cell Membranes.

    Science.gov (United States)

    Aricò, Antonino S; Sebastian, David; Schuster, Michael; Bauer, Bernd; D'Urso, Claudia; Lufrano, Francesco; Baglio, Vincenzo

    2015-11-24

    Sulfonic acid-functionalized polymer electrolyte membranes alternative to Nafion(®) were developed. These were hydrocarbon systems, such as blend sulfonated polyetheretherketone (s-PEEK), new generation perfluorosulfonic acid (PFSA) systems, and composite zirconium phosphate-PFSA polymers. The membranes varied in terms of composition, equivalent weight, thickness, and filler and were investigated with regard to their methanol permeation characteristics and proton conductivity for application in direct methanol fuel cells. The behavior of the membrane electrode assemblies (MEA) was investigated in fuel cell with the aim to individuate a correlation between membrane characteristics and their performance in a direct methanol fuel cell (DMFC). The power density of the DMFC at 60 °C increased according to a square root-like function of the membrane selectivity. This was defined as the reciprocal of the product between area specific resistance and crossover. The power density achieved at 60 °C for the most promising s-PEEK-based membrane-electrode assembly (MEA) was higher than the benchmark Nafion(®) 115-based MEA (77 mW·cm(-2) vs. 64 mW·cm(-2)). This result was due to a lower methanol crossover (47 mA·cm(-2) equivalent current density for s-PEEK vs. 120 mA·cm(-2) for Nafion(®) 115 at 60 °C as recorded at OCV with 2 M methanol) and a suitable area specific resistance (0.15 Ohm cm² for s-PEEK vs. 0.22 Ohm cm² for Nafion(®) 115).

  14. Methanol production from Eucalyptus wood chips. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Fishkind, H.H.

    1982-06-01

    This feasibility study includes all phases of methanol production from seedling to delivery of finished methanol. The study examines: production of 55 million, high quality, Eucalyptus seedlings through tissue culture; establishment of a Eucalyptus energy plantation on approximately 70,000 acres; engineering for a 100 million gallon-per-day methanol production facility; potential environmental impacts of the whole project; safety and health aspects of producing and using methanol; and development of site specific cost estimates.

  15. Environmental Transmission Electron Microscopy of catalysts for the methanol synthesis

    DEFF Research Database (Denmark)

    Duchstein, Linus Daniel Leonhard

    Everywhere around the world, natural resources like crude oil are becoming less and harder to extract. It is therefore necessary to find alternatives to secure our future transportation in a sustainable way. This can be done e.g. through chemical conversion of lignocelluloses into bio...... and the reaction of the catalysts as they were happening and study crystal phase changes as well as chemical shifts because the instruments are capable of introducing gases around the sample while still maintaining their investigation properties. It could be shown, that NiGa forms Ni5Ga3nanoparticles while Cu...... to scale with the beam current density but foremost with the exposure time. The ETEM shows phase and chemical changes during the reaction....

  16. An Analysis of Methanol and Hydrogen Production via High-Temperature Electrolysis Using the Sodium Cooled Advanced Fast Reactor

    Energy Technology Data Exchange (ETDEWEB)

    Shannon M. Bragg-Sitton; Richard D. Boardman; Robert S. Cherry; Wesley R. Deason; Michael G. McKellar

    2014-03-01

    Integration of an advanced, sodium-cooled fast spectrum reactor into nuclear hybrid energy system (NHES) architectures is the focus of the present study. A techno-economic evaluation of several conceptual system designs was performed for the integration of a sodium-cooled Advanced Fast Reactor (AFR) with the electric grid in conjunction with wind-generated electricity. Cases in which excess thermal and electrical energy would be reapportioned within an integrated energy system to a chemical plant are presented. The process applications evaluated include hydrogen production via high temperature steam electrolysis and methanol production via steam methane reforming to produce carbon monoxide and hydrogen which feed a methanol synthesis reactor. Three power cycles were considered for integration with the AFR, including subcritical and supercritical Rankine cycles and a modified supercritical carbon dioxide modified Brayton cycle. The thermal efficiencies of all of the modeled power conversions units were greater than 40%. A thermal efficiency of 42% was adopted in economic studies because two of the cycles either performed at that level or could potentially do so (subcritical Rankine and S-CO2 Brayton). Each of the evaluated hybrid architectures would be technically feasible but would demonstrate a different internal rate of return (IRR) as a function of multiple parameters; all evaluated configurations showed a positive IRR. As expected, integration of an AFR with a chemical plant increases the IRR when “must-take” wind-generated electricity is added to the energy system. Additional dynamic system analyses are recommended to draw detailed conclusions on the feasibility and economic benefits associated with AFR-hybrid energy system operation.

  17. Experimental analysis of methanol cross-over in a direct methanol fuel cell

    Energy Technology Data Exchange (ETDEWEB)

    Casalegno, Andrea [Dipartimento di Energetica, Politecnico di Milano, Piazza Leonardo da Vinci 32, 20133 Milan (Italy)]. E-mail: andrea.casalegno@polimi.it; Grassini, Paolo [Dipartimento di Energetica, Politecnico di Milano, Piazza Leonardo da Vinci 32, 20133 Milan (Italy)]. E-mail: PGrassini@seal.it; Marchesi, Renzo [Dipartimento di Energetica, Politecnico di Milano, Piazza Leonardo da Vinci 32, 20133 Milan (Italy)]. E-mail: renzo.marchesi@polimi.it

    2007-03-15

    Methanol cross-over through the polymeric membrane is one of the main causes limiting direct methanol fuel cell performances. It causes fuel wasting and enhances cathode overpotential. A repeatable and reproducible measurement system, that assures the traceability of the measurement to international reference standards, is necessary to compare different fuel cell construction materials. In this work a method to evaluate methanol cross-over rate and operating condition influence is presented and qualified in term of measurement uncertainty. In the investigated range, the methanol cross-over rate results mainly due to diffusion through the membrane, in fact it is strongly affected by temperature. Moreover the cross-over influence on fuel utilization and fuel cell efficiency is investigated. The methanol cross-over rate appears linearly proportional to electrochemical fuel utilization and values, obtained by measurements at different anode flow rate but constant electrochemical fuel utilization, are roughly equal; methanol wasting, due to cross-over, is considerable and can still be higher than electrochemical utilization. The fuel recirculation effect on energy efficiency has been investigated and it was found that fuel recirculation gives more advantage at low temperature, but fuel cell energy efficiency results are in any event higher at high temperature.

  18. Experimental analysis of methanol cross-over in a direct methanol fuel cell

    International Nuclear Information System (INIS)

    Casalegno, Andrea; Grassini, Paolo; Marchesi, Renzo

    2007-01-01

    Methanol cross-over through the polymeric membrane is one of the main causes limiting direct methanol fuel cell performances. It causes fuel wasting and enhances cathode overpotential. A repeatable and reproducible measurement system, that assures the traceability of the measurement to international reference standards, is necessary to compare different fuel cell construction materials. In this work a method to evaluate methanol cross-over rate and operating condition influence is presented and qualified in term of measurement uncertainty. In the investigated range, the methanol cross-over rate results mainly due to diffusion through the membrane, in fact it is strongly affected by temperature. Moreover the cross-over influence on fuel utilization and fuel cell efficiency is investigated. The methanol cross-over rate appears linearly proportional to electrochemical fuel utilization and values, obtained by measurements at different anode flow rate but constant electrochemical fuel utilization, are roughly equal; methanol wasting, due to cross-over, is considerable and can still be higher than electrochemical utilization. The fuel recirculation effect on energy efficiency has been investigated and it was found that fuel recirculation gives more advantage at low temperature, but fuel cell energy efficiency results are in any event higher at high temperature

  19. Preparation of Biomorphic SiC/C Ceramics from Pine Wood via Supercritical Ethanol Infiltration

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    Biomorphic (wood derived) carbide ceramics with an overall composition in the SiC/C was produced by supercritical ethanol infiltration of low viscosity tetraethylorthosilicate/supercritical ethanol into biologically derived carbon templates (CB-templates) and in situ hydrolysis into Si(OH)4-gel, the Si(OH)4-gel was calcined at 1400℃ to promote the polycondensation of Si(OH)4-gel into SiO2-phase and then carbonthermal reduction of the SiO2 with the biocarbon template into highly porous, biomorphic SiC/C ceramics. The phases and morphology conversion mechanism of resulting porous SiC/C ceramics have been investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and Fourier transform infrared spectroscopy (FT-IR). Experimental results showed that the biomorphic cellular morphology of pinewood charcoal was remained in the porous SiC/C ceramic with high precision that consisted of β-SiC with minority of α-SiC and the remain free carbon existed in amorphous phase.

  20. A Review of Study on Thermal Energy Transport System by Synthesis and Decomposition Reactions of Methanol

    Science.gov (United States)

    Liu, Qiusheng; Yabe, Akira; Kajiyama, Shiro; Fukuda, Katsuya

    -phase chemical reaction by varying the development time of the catalyst. Investigation results of the catalyst such as surface area, pore radius, lattice size, and photographs of scanning electron microscope (SEM) were also given. In the simulation of energy transport efficiency of this system, by simulating the energy transfer system using two-step liquid phase methanol decomposition and synthetic reactions, and comparing with the technology so far, it can be expected that an innovative energy transfer system is possible to realize.

  1. Process and catalysts for the gasification of methanol. [German Patent

    Energy Technology Data Exchange (ETDEWEB)

    Harris, N.; Dennis, A.J.; Shevels, T.F.

    1975-02-13

    The invention concerns catalysts and catalytic processes for the gasification of methanol which is used to manufacture methane from methanol. Mixtures of iron and chromium oxide, phosphate, phosphoric acid, tungstate, tungstic acid, aluminium phosphate, aluminium oxide are suitable as dehydrating catalysts. Gasification takes place together with steam and dehydrogenating catalysts at high temperature. The molar ratios steam: methanol are described.

  2. FORMALDEHYDE DISMUTASE ACTIVITIES IN GRAM-POSITIVE BACTERIA OXIDIZING METHANOL

    NARCIS (Netherlands)

    BYSTRYKH, LV; GOVORUKHINA, NI; VANOPHEM, PW; HEKTOR, HJ; DIJKHUIZEN, L; DUINE, JA; Govorukhina, Natalya; Ophem, Peter W. van; Duine, Johannis A.

    Extracts of methanol-grown cells of Amycolatopsis methanolica and Mycobacterium gastri oxidized methanol and ethanol with concomitant reduction of N,N'-dimethyl-4-nitrosoaniline (NDMA). Anion-exchange chromatography revealed the presence of a single enzyme able to catalyse this activity in methanol-

  3. Acidities of Water and Methanol in Aqueous Solution and DMSO

    Science.gov (United States)

    Gao, Daqing

    2009-01-01

    The relative acidities of water and methanol have been a nagging issue. In gas phase, methanol is more acidic than water by 36.0 kJ/mol; however, in aqueous solution, the acidities of methanol and water are almost identical. The acidity of an acid in solution is determined by both the intrinsic gas-phase ionization Gibbs energy and the solvent…

  4. Comparison between constant methanol feed and on-line ...

    African Journals Online (AJOL)

    Two methanol feeding methods, namely constant methanol feed and on-line monitoring feed control by methanol sensor were investigated to improve the production of recombinant human growth hormone (rhGH) in high cell density cultivation of Pichia pastoris KM71 in 2 L bioreactor. The yeast utilized glycerol as a carbon ...

  5. Recent Advances in High-Performance Direct Methanol Fuel Cells

    Science.gov (United States)

    Narayanan, S. R.; Chun, W.; Valdez, T. I.; Jeffries-Nakamura, B.; Frank, H.; Surumpudi, S.; Halpert, G.; Kosek, J.; Cropley, C.; La Conti, A. B.; hide

    1996-01-01

    Direct methanol fuel cells for portable power applications have been advanced significantly under DARPA- and ARO-sponsored programs over the last five years. A liquid-feed, direct methanol fuel cell developed under these programs, employs a proton exchange membrane as electrolyte and operates on aqueous solutions of methanol with air or oxygen as the oxidant.

  6. Biological activities of Rumex dentatus L: Evaluation of methanol ...

    African Journals Online (AJOL)

    The methanol extracts of leaf and stem inhibited radish seed germination (70 and 61% respectively) and root length more than the hexane extracts. The R. dentatus methanol extract showed presence of alkaloids, saponins, anthraquinones and tannins while flavonoids were also found in both methanol as well as hexane ...

  7. Solid-state flurbiprofen and methyl-β-cyclodextrin inclusion complexes prepared using a single-step, organic solvent-free supercritical fluid process.

    Science.gov (United States)

    Rudrangi, Shashi Ravi Suman; Kaialy, Waseem; Ghori, Muhammad U; Trivedi, Vivek; Snowden, Martin J; Alexander, Bruce David

    2016-07-01

    The aim of this study was to enhance the apparent solubility and dissolution properties of flurbiprofen through inclusion complexation with cyclodextrins. Especially, the efficacy of supercritical fluid technology as a preparative technique for the preparation of flurbiprofen-methyl-β-cyclodextrin inclusion complexes was evaluated. The complexes were prepared by supercritical carbon dioxide processing and were evaluated by solubility, differential scanning calorimetry, X-ray powder diffraction, scanning electron microscopy, practical yield, drug content estimation and in vitro dissolution studies. Computational molecular docking studies were conducted to study the possibility of molecular arrangement of inclusion complexes between flurbiprofen and methyl-β-cyclodextrin. The studies support the formation of stable molecular inclusion complexes between the drug and cyclodextrin in a 1:1 stoichiometry. In vitro dissolution studies showed that the dissolution properties of flurbiprofen were significantly enhanced by the binary mixtures prepared by supercritical carbon dioxide processing. The amount of flurbiprofen dissolved into solution alone was very low with 1.11±0.09% dissolving at the end of 60min, while the binary mixtures processed by supercritical carbon dioxide at 45°C and 200bar released 99.39±2.34% of the drug at the end of 30min. All the binary mixtures processed by supercritical carbon dioxide at 45°C exhibited a drug release of more than 80% within the first 10min irrespective of the pressure employed. The study demonstrated the single step, organic solvent-free supercritical carbon dioxide process as a promising approach for the preparation of inclusion complexes between flurbiprofen and methyl-β-cyclodextrin in solid-state. Copyright © 2016 Elsevier B.V. All rights reserved.

  8. Effects of Supercritical CO 2 Conditioning on Cross-Linked Polyimide Membranes

    KAUST Repository

    Kratochvil, Adam M.; Koros, William J.

    2010-01-01

    The effects of supercritical CO2 (scCO2) conditioning on high-performance cross-linked polyimide membranes is examined through gas permeation and sorption experiments. Under supercritical conditions, the cross-linked polymers do not exhibit a

  9. SUPERCRITICAL FLUID EXTRACTION OF POLYCYCLIC AROMATIC HYDROCARBON MIXTURES FROM CONTAMINATED SOILS

    Science.gov (United States)

    Highly contaminated (with PAHs) topsoils were extracted with supercritical CO2 to determine the feasibility and mechanism of supercritical fluid extraction (SFE). Effect of SCF density, temperature, cosolvent type and amount, and of slurrying the soil with water were ...

  10. The deep-subsurface sulfate reducer Desulfotomaculum kuznetsovii employs two methanol-degrading pathways

    NARCIS (Netherlands)

    Sousa, Diana Z.; Visser, Michael; Gelder, Van Antonie H.; Boeren, Sjef; Pieterse, Mervin M.; Pinkse, Martijn W.H.; Verhaert, Peter D.E.M.; Vogt, Carsten; Franke, Steffi; Kümmel, Steffen; Stams, Alfons J.M.

    2018-01-01

    Methanol is generally metabolized through a pathway initiated by a cobalamine-containing methanol methyltransferase by anaerobic methylotrophs (such as methanogens and acetogens), or through oxidation to formaldehyde using a methanol dehydrogenase by aerobes. Methanol is an important substrate in

  11. Preparation of Carbon-Platinum-Ceria and Carbon-Platinum-Cerium catalysts and its application in Polymer Electrolyte Fuel Cell: Hydrogen, Methanol, and Ethanol

    Science.gov (United States)

    Guzman Blas, Rolando Pedro

    This thesis is focused on fuel cells using hydrogen, methanol and ethanol as fuel. Also, in the method of preparation of catalytic material for the anode: Supercritical Fluid Deposition (SFD) and impregnation method using ethylenediaminetetraacetic acid (EDTA) as a chelating agent. The first part of the thesis describes the general knowledge about Hydrogen Polymer Exchange Membrane Fuel Cell (HPEMFC),Direct Methanol Fuel Cell (DMFC) and Direct Ethanol Fuel Cell (DEFC), as well as the properties of Cerium and CeO2 (Ceria). The second part of the thesis describes the preparation of catalytic material by Supercritical Fluid Deposition (SFD). SFD was utilized to deposit Pt and ceria simultaneously onto gas diffusion layers. The Pt-ceria catalyst deposited by SFD exhibited higher methanol oxidation activity compared to the platinum catalyst alone. The linear sweep traces of the cathode made for the methanol cross over study indicate that Pt-Ceria/C as the anode catalyst, due to its better activity for methanol, improves the fuel utilization, minimizing the methanol permeation from anode to cathode compartment. The third and fourth parts of the thesis describe the preparation of material catalytic material Carbon-Platinum-Cerium by a simple and cheap impregnation method using EDTA as a chelating agent to form a complex with cerium (III). This preparation method allows the mass production of the material catalysts without additional significant cost. Fuel cell polarization and power curves experiments showed that the Carbon-Platinum-Cerium anode materials exhibited better catalytic activity than the only Vulcan-Pt catalysts for DMFC, DEFC and HPEMFC. In the case of Vulcan-20%Pt-5%w Cerium, this material exhibits better catalytic activity than the Vulcan-20%Pt in DMFC. In the case of Vulcan-40% Pt-doped Cerium, this material exhibits better catalytic activity than the Vulcan-40% Pt in DMFC, DEFC and HPEMFC. Finally, I propose a theory that explains the reason why the

  12. Development of Nuclear Decontamination Technology Using Supercritical Fluid

    International Nuclear Information System (INIS)

    Jung, Wonyoung; Park, Kwangheon; Park, Jihye; Lee, Donghee

    2014-01-01

    Soil cleaning technologies that have been developed thus far increase treatment costs in contaminated soil recovery processes because they generate large amounts of secondary wastes. In this respect, this study is intended to develop soil decontamination methods using CO 2 , which is a nontoxic, environmentally friendly substance, in order to fundamentally suppress the generation of secondary wastes from the decontamination process and to create high added values. In this study, to develop decontamination methods for uranium-contaminated soil using supercritical CO 2 , a soil decontamination system using supercritical CO 2 was constructed. In addition, the basic principle of supercritical CO 2 decontamination using a TBP-HNO3 complex was explained. According to the results of the study, sea-sand samples having the same degree of contamination showed different results of decontamination according to the quantities of the TBP-HNO3 complex used as an extraction agent, which resulted in high extraction rates. Thus far, a most widely used method of extracting uranium has been the dissolving of uranium in acids. However, this method has the large adverse effect of generating strong acidic wastes that cannot be easily treated. On the other hand, supercritical CO 2 requires critical conditions that are no more difficult to meet than those of other supercritical fluids, since its density can be changed from a very low state close to that of an ideal gas to a high state close to that of liquids. The critical gas conditions are a pressure of 71 bar and a temperature of 31 .deg. C, both of which are inexpensive to achieve. Moreover, CO 2 is a solvent that is not harmful to the human body and few effects on environmental pollution. Therefore, nontoxic and environment friendly processes can be developed using supercritical CO 2 . Supercritical CO 2 's advantages over prevailing methods suggest its potential for developing innovative decontamination methods, as demonstrated

  13. Resonances in positron scattering on a supercritical nucleus and spontaneous production of e{sup +}e{sup -} pairs

    Energy Technology Data Exchange (ETDEWEB)

    Godunov, S.I. [National Research Centre Kurchatov Institute, Alikhanov Institute for Theoretical and Experimental Physics, Moscow (Russian Federation); Novosibirsk State University, Novosibirsk (Russian Federation); Machet, B. [Sorbonne Universites, LPTHE, Universite P. et M. Curie, Paris (France); CNRS, UMR 7589, LPTHE, Paris (France); Vysotsky, M.I. [National Research Centre Kurchatov Institute, Alikhanov Institute for Theoretical and Experimental Physics, Moscow (Russian Federation); National Research University Higher School of Economics, Moscow (Russian Federation)

    2017-11-15

    We re-examine the physics of supercritical nuclei, specially focusing on the scattering phase δ{sub κ} and its dependence on the energy ε of the diving electronic level, for which we give both exact and approximate formulas. The Coulomb potential Zα/r is rounded to the constant Zα/R for r < R. We confirm the resonant behavior of δ{sub κ} that we investigate in detail. In addition to solving the Dirac equation for an electron, we solve it for a positron, in the field of the same nucleus. This clarifies the interpretation of the resonances. Our results are compared with claims made in previous works. (orig.)

  14. Zeolite-Catalyzed Hydrocarbon Formation from Methanol: Density Functional Simulations

    Directory of Open Access Journals (Sweden)

    George Fitzgerald

    2002-04-01

    Full Text Available Abstract: We report detailed density functional theory (DFT calculations of important mechanisms in the methanol to gasoline (MTG process in a zeolite catalyst. Various reaction paths and energy barriers involving C-O bond cleavage and the first C-C bond formation are investigated in detail using all-electron periodic supercell calculations and recently developed geometry optimization and transition state search algorithms. We have further investigated the formation of ethanol and have identified a different mechanism than previously reported [1], a reaction where water does not play any visible role. Contrary to recent cluster calculations, we were not able to find a stable surface ylide structure. However, a stable ylide structure built into the zeolite framework was found to be possible, albeit a very high reaction barrier.

  15. Development of an electrode for direct methanol fuel cell

    International Nuclear Information System (INIS)

    Ramzia, A. M. S.; Iqbal, J.

    2006-01-01

    This paper presents the efficient use of platinum catalyst ruthenium with in the anode of a Direct Methanol Fuel Cell (DMFC). This is achieved by depositing platinum and ruthenium nano-particles on the pre-refluxed multi-walled carbon nano-tubes (MWCNT): MWCNTs were synthesized using the Chemical Vapor Deposition (CVD) with floating catalyst technique. The synthesized carbon nano tubes (CNT) were refluxed in 12M nitric acid to produce anchoring sites on the surface of the CNT. The platinum and ruthenium nano-particles were in a ratio of (3.1). These particles are deposited on the surface of the CNT at 60 wt % by reduction in ethylene glycol. Transmission micrograph (TEM) and scanning electron micrograph (SEM) images show the success of the deposition method. (author)

  16. Degradation of brominated flame retardant in computer housing plastic by supercritical fluids.

    Science.gov (United States)

    Wang, Yanmin; Zhang, Fu-Shen

    2012-02-29

    The degradation process of brominated flame retardant (BFR) and BFR-containing waste computer housing plastic in various supercritical fluids (water, methanol, isopropanol and acetone) was investigated. The results showed that the debromination and degradation efficiencies, final products were greatly affected by the solvent type. Among the four tested solvents, isopropanol was the most suitable solvent for the recovery of oil from BFR-containing plastic for its (1) excellent debromination effectiveness (debromination efficiency 95.7%), (2) high oil production (60.0%) and (3) mild temperature and pressure requirements. However, in this case, the removed bromine mostly existed in the oil. Introduction of KOH into the sc-isopropanol could capture almost all the inorganic bromine from the oil thus bromine-free oil could be obtained. Furthermore, KOH could enhance the depolymerization of the plastic. The obtained oil mainly consisted of single- and duplicate-ringed aromatic compounds in a carbon range of C9-C17, which had alkyl substituents or aliphatic bridges, such as butyl-benzene, (3-methylbutyl)-benzene, 1,1'-(1,3-propanediyl)bis benzene. Phenol, alkyl phenols and esters were the major oxygen-containing compounds in the oil. This study provides an efficient approach for debromination and simultaneous recovering valuable chemicals from BFR-containing plastic in e-waste. Copyright © 2011 Elsevier B.V. All rights reserved.

  17. A novel gaseous pinacolyl alcohol sensor utilizing cataluminescence on alumina nanowires prepared by supercritical fluid drying.

    Science.gov (United States)

    Yu, Chao; Liu, Guohong; Zuo, Boli; Tang, Yongjun; Zhang, Tian

    2008-06-23

    A cataluminescence (CTL) sensor using Al2O3 nanowires as the sensing material was developed for the determination of trace pinacolyl alcohol in air samples based on the catalytic chemiluminescence (CL) of pinacolyl alcohol on Al2O3 nanowires. Eight catalysts were examined and the CL intensity on Al2O3 nanowires prepared by supercritical fluid drying was the strongest. This novel CL sensor showed high sensitivity and selectivity to gaseous pinacolyl alcohol at optimal temperature of 340 degrees C. Quantitative analysis was performed at a wavelength of 460 nm. The linear range of CTL intensity versus concentration of gaseous pinacolyl alcohol was 0.09 x 10(-6) to 2.56 x 10(-6) g mL(-1) (r=0.9983, n=6) with a detection limit (3 sigma) of 0.0053 x 10(-6) g mL(-1). None or only very low levels of interference were observed while the foreign substances such as water vapor, ethanol, ammonia, chloroform, benzene, nitrogen dioxide, methylbenzene, hydrochloric acid, methanol and butanol were passing through the sensor. The response time of the sensor is less than 100 s, and the sensor had a long lifetime more than 60 h. The sensor would be potentially applied to analysis of the nerve agents such as Soman.

  18. Possibilities and limitations of the kinetic plot method in supercritical fluid chromatography.

    Science.gov (United States)

    De Pauw, Ruben; Desmet, Gert; Broeckhoven, Ken

    2013-08-30

    Although supercritical fluid chromatography (SFC) is becoming a technique of increasing importance in the field of analytical chromatography, methods to compare the performance of SFC-columns and separations in an unbiased way are not fully developed. The present study uses mathematical models to investigate the possibilities and limitations of the kinetic plot method in SFC as this easily allows to investigate a wide range of operating pressures, retention and mobile phase conditions. The variable column length (L) kinetic plot method was further investigated in this work. Since the pressure history is identical for each measurement, this method gives the true kinetic performance limit in SFC. The deviations of the traditional way of measuring the performance as a function of flow rate (fixed back pressure and column length) and the isopycnic method with respect to this variable column length method were investigated under a wide range of operational conditions. It is found that using the variable L method, extrapolations towards other pressure drops are not valid in SFC (deviation of ∼15% for extrapolation from 50 to 200bar pressure drop). The isopycnic method provides the best prediction but its use is limited when operating closer towards critical point conditions. When an organic modifier is used, the predictions are improved for both methods with respect to the variable L method (e.g. deviations decreases from 20% to 2% when 20mol% of methanol is added). Copyright © 2013 Elsevier B.V. All rights reserved.

  19. A novel technique for hydrogen production from hog-manure in supercritical partial oxidation (SCWPO)

    Energy Technology Data Exchange (ETDEWEB)

    Youssef, Emhemmed A.; Charpentier, Paul [Western Ontario Univ., London, ON (Canada). Dept. of Chemical and Biochemical Engineering; Nakhla, George [Western Ontario Univ., London, ON (Canada). Dept. of Chemical and Biochemical Engineering; Western Ontario Univ., London, ON (Canada). Dept. of Civil and Environmental Engineering; Elbeshbishy, Elsayed; Hafez, Hisham [Western Ontario Univ., London, ON (Canada). Dept. of Civil and Environmental Engineering

    2010-07-01

    In this study, the catalytic hydrogen production from hog manure using supercritical water partial oxidation was investigated in a batch reactor at a temperature of 500 C, and pressure of 28 MPa using several metallic catalysts. Hog manure was characterized by a total and soluble chemical oxygen demand (TCOD, SCOD) of 57000 and 28000 mg/L, total and volatile suspended solids (TSS, VSS) of 25000, 19000, and ammonia of 2400 mg/L, respectively. The order of H{sub 2} production was the following: Pd/AC > Ru/Al{sub 2}O{sub 3} > Ru/AC > AC > NaOH. The order of COD reduction efficiency was as follows: NaOH > Ru/AC > AC > Ru/Al{sub 2}O{sub 3} > Pd/AC. The behaviour of the volatile fatty acids (VFA's), ethanol, methanol, ammonia, H{sub 2}S, and Sulfate was investigated experimentally and discussed. A 35 % reduction in the H{sub 2} and CH{sub 4} yields was observed in the sequential gasification partial oxidation (oxidant at an 80 % of theoretical requirement) experiments compared to the gasification experiments (catalyst only). Moreover, this reduction in gas yields was coincided with a 45 % reduction in the liquid effluent chemical oxygen demand (COD), 60 % reduction of the ammonia concentration in the liquid effluent, and 20 % reduction in the H{sub 2}S concentration in the effluent gas. (orig.)

  20. Computational fluid dynamics study of viscous fingering in supercritical fluid chromatography.

    Science.gov (United States)

    Subraveti, Sai Gokul; Nikrityuk, Petr; Rajendran, Arvind

    2018-01-26

    Axi-symmetric numerical simulations are carried out to study the dynamics of a plug introduced through a mixed-stream injection in supercritical fluid chromatographic columns. The computational fluid dynamics model developed in this work takes into account both the hydrodynamics and adsorption equilibria to describe the phenomena of viscous fingering and plug effect that contribute to peak distortions in mixed-stream injections. The model was implemented into commercial computational fluid dynamics software using user-defined functions. The simulations describe the propagation of both the solute and modifier highlighting the interplay between the hydrodynamics and plug effect. The simulated peaks showed good agreement with experimental data published in the literature involving different injection volumes (5 μL, 50 μL, 1 mL and 2 mL) of flurbiprofen on Chiralpak AD-H column using a mobile phase of CO 2 and methanol. The study demonstrates that while viscous fingering is the main source of peak distortions for large-volume injections (1 mL and 2 mL) it has negligible impact on small-volume injections (5 μL and 50 μL). Band broadening in small-volume injections arise mainly due to the plug effect. Crown Copyright © 2017. Published by Elsevier B.V. All rights reserved.

  1. Enantioselective potential of polysaccharide-based chiral stationary phases in supercritical fluid chromatography.

    Science.gov (United States)

    Kucerova, Gabriela; Kalikova, Kveta; Tesarova, Eva

    2017-06-01

    The enantioselective potential of two polysaccharide-based chiral stationary phases for analysis of chiral structurally diverse biologically active compounds was evaluated in supercritical fluid chromatography using a set of 52 analytes. The chiral selectors immobilized on 2.5 μm silica particles were tris-(3,5-dimethylphenylcarmabate) derivatives of cellulose or amylose. The influence of the polysaccharide backbone, different organic modifiers, and different mobile phase additives on retention and enantioseparation was monitored. Conditions for fast baseline enantioseparation were found for the majority of the compounds. The success rate of baseline and partial enantioseparation with cellulose-based chiral stationary phase was 51.9% and 15.4%, respectively. Using amylose-based chiral stationary phase we obtained 76.9% of baseline enantioseparations and 9.6% of partial enantioseparations of the tested compounds. The best results on cellulose-based chiral stationary phase were achieved particularly with propane-2-ol and a mixture of isopropylamine and trifluoroacetic acid as organic modifier and additive to CO 2 , respectively. Methanol and basic additive isopropylamine were preferred on amylose-based chiral stationary phase. The complementary enantioselectivity of the cellulose- and amylose-based chiral stationary phases allows separation of the majority of the tested structurally different compounds. Separation systems were found to be directly applicable for analyses of biologically active compounds of interest. © 2017 Wiley Periodicals, Inc.

  2. Development of a sensitive and rapid method for rifampicin impurity analysis using supercritical fluid chromatography.

    Science.gov (United States)

    Li, Wei; Wang, Jun; Yan, Zheng-Yu

    2015-10-10

    A novel simple, fast and efficient supercritical fluid chromatography (SFC) method was developed and compared with RPLC method for the separation and determination of impurities in rifampicin. The separation was performed using a packed diol column and a mobile phase B (modifier) consisting of methanol with 0.1% ammonium formate (w/v) and 2% water (v/v). Overall satisfactory resolutions and peak shapes for rifampicin quinone (RQ), rifampicin (RF), rifamycin SV (RSV), rifampicin N-oxide (RNO) and 3-formylrifamycinSV (3-FR) were obtained by optimization of the chromatography system. With gradient elution of mobile phase, all of the impurities and the active were separated within 4 min. Taking full advantage of features of SFC (such as particular selectivity, non-sloping baseline in gradient elution, and without injection solvent effects), the method was successfully used for determination of impurities in rifampicin, with more impurity peaks detected, better resolution achieved and much less analysis time needed compared with conventional reversed-phase liquid chromatography (RPLC) methods. Copyright © 2015 Elsevier B.V. All rights reserved.

  3. Quantitative determination of major alkaloids in Cinchona bark by Supercritical Fluid Chromatography.

    Science.gov (United States)

    Murauer, Adele; Ganzera, Markus

    2018-06-15

    Chinoline alkaloids found in Cinchona bark still play an important role in medicine, for example as antimalarial and antiarrhythmic drugs. For the first time Supercritical Fluid Chromatography has been utilized for their separation. Six respective derivatives (dihydroquinidine, dihydroquinine, quinidine, quinine, cinchonine and cinchonidine) could be resolved in less than 7 min, and three of them quantified in crude plant extracts. The optimum stationary phase showed to be an Acquity UPC 2 Torus DEA 1.7 μm column, the mobile phase comprised of CO 2 , acetonitrile, methanol and diethylamine. Method validation confirmed that the procedure is selective, accurate (recovery rates from 97.2% to 103.7%), precise (intra-day ≤2.2%, inter-day ≤3.0%) and linear (R 2  ≥ 0.999); at 275 nm the observed detection limits were always below 2.5 μg/ml. In all of the samples analyzed cinchonine dominated (1.87%-2.30%), followed by quinine and cinchonidine. Their total content ranged from 4.75% to 5.20%. These values are in good agreement with published data, so that due to unmatched speed and environmental friendly character SFC is definitely an excellent alternative for the analysis of these important natural products. Copyright © 2018 The Author(s). Published by Elsevier B.V. All rights reserved.

  4. Supercritical Fluid Extraction of Bacterial and Archaeal Lipid Biomarkers from Anaerobically Digested Sludge

    Directory of Open Access Journals (Sweden)

    Koichi Fujie

    2012-03-01

    Full Text Available Supercritical fluid extraction (SFE was used in the analysis of bacterial respiratory quinone (RQ, bacterial phospholipid fatty acid (PLFA, and archaeal phospholipid ether lipid (PLEL from anaerobically digested sludge. Bacterial RQ were determined using ultra performance liquid chromatography (UPLC. Determination of bacterial PLFA and archaeal PLEL was simultaneously performed using gas chromatography-mass spectrometry (GC-MS. The effects of pressure, temperature, and modifier concentration on the total amounts of RQ, PLFA, and PLEL were investigated by 23 experiments with five settings chosen for each variable. The optimal extraction conditions that were obtained through a multiple-response optimization included a pressure of 23.6 MPa, temperature of 77.6 °C, and 10.6% (v/v of methanol as the modifier. Thirty nine components of microbial lipid biomarkers were identified in the anaerobically digested sludge. Overall, the SFE method proved to be more effective, rapid, and quantitative for simultaneously extracting bacterial and archaeal lipid biomarkers, compared to conventional organic solvent extraction. This work shows the potential application of SFE as a routine method for the comprehensive analysis of microbial community structures in environmental assessments using the lipid biomarkers profile.

  5. Compact Fuel-Cell System Would Consume Neat Methanol

    Science.gov (United States)

    Narayanan, Sekharipuram; Kindler, Andrew; Valdez, Thomas

    2007-01-01

    In a proposed direct methanol fuel-cell electric-power-generating system, the fuel cells would consume neat methanol, in contradistinction to the dilute aqueous methanol solutions consumed in prior direct methanol fuel-cell systems. The design concept of the proposed fuel-cell system takes advantage of (1) electro-osmotic drag and diffusion processes to manage the flows of hydrogen and water between the anode and the cathode and (2) evaporative cooling for regulating temperature. The design concept provides for supplying enough water to the anodes to enable the use of neat methanol while ensuring conservation of water for the whole fuel-cell system.

  6. Enhancement of the dissolution rate and bioavailability of fenofibrate by a melt-adsorption method using supercritical carbon dioxide

    Directory of Open Access Journals (Sweden)

    Cha KH

    2012-10-01

    Full Text Available Kwang-Ho Cha,1,3 Kyung-Jin Cho,3 Min-Soo Kim,4 Jeong-Soo Kim,3 Hee Jun Park,1,3 Junsung Park,1,3 Wonkyung Cho,1,3 Jeong-Sook Park,3 Sung-Joo Hwang1,21Yonsei Institute of Pharmaceutical Sciences, 2College of Pharmacy, Yonsei University, Incheon, Republic of Korea; 3College of Pharmacy, Chungnam National University, Daejeon, Republic of Korea; 4Department of Pharmaceutical Engineering, Inje University, Gimhae, Republic of KoreaBackground: The aim of this study was to enhance the bioavailability of fenofibrate, a poorly water-soluble drug, using a melt-adsorption method with supercritical CO2.Methods: Fenofibrate was loaded onto Neusilin® UFL2 at different weight ratios of fenofibrate to Neusilin UFL2 by melt-adsorption using supercritical CO2. For comparison, fenofibrate-loaded Neusilin UFL2 was prepared by solvent evaporation and hot melt-adsorption methods. The fenofibrate formulations prepared were characterized by differential scanning calorimetry, powder x-ray diffractometry, specific surface area, pore size distribution, scanning electron microscopy, and energy-dispersive x-ray spectrometry. In vitro dissolution and in vivo bioavailability were also investigated.Results: Fenofibrate was distributed into the pores of Neusilin UFL2 and showed reduced crystal formation following adsorption. Supercritical CO2 facilitated the introduction of fenofibrate into the pores of Neusilin UFL2. Compared with raw fenofibrate, fenofibrate from the prepared powders showed a significantly increased dissolution rate and better bioavailability. In particular, the area under the drug concentration-time curve and maximal serum concentration of the powders prepared using supercritical CO2 were 4.62-fold and 4.52-fold greater than the corresponding values for raw fenofibrate.Conclusion: The results of this study highlight the usefulness of the melt-adsorption method using supercritical CO2 for improving the bioavailability of fenofibrate.Keywords: fenofibrate

  7. High performance supercapacitor using N-doped graphene prepared via supercritical fluid processing with an oxime nitrogen source

    International Nuclear Information System (INIS)

    Balaji, S. Suresh; Elavarasan, A.; Sathish, M.

    2016-01-01

    Graphical abstract: N-doped graphene prepared via supercritical fluid processing with oxime nitrogen source (DMG) showed enhanced performance in electrochemical supercapacitor application. A maximum specific capacitance of 286 F g"−"1 at a current density of 0.5 A/g was achieved with a high specific capacity retention of 98% after 1000 cycles at 5 A/g. - Highlights: • N-functionalised graphene synthesized via supercritical fluid processing. • DMG, an oxime based nitrogen precursor. • Maximum specific capacitance of 286 F/g at 0.5 A/g in aqueous solution. • Pyridinic as well as quarternary nitrogen for enhanced capacitance. - Abstract: Heteroatom doped graphene has been proved for its promising applications in electrochemical energy storage systems. Here, nitrogen (N) doped graphene was prepared via two different techniques namely supercritical fluid assisted processing and hydrothermal heat treatment using dimethylglyoxime (DMG) as an oxime nitrogen precursor. The FT-IR and Raman spectra showed the N-containing functional group in the graphene. The XRD analysis revealed the complete reduction of graphene oxide during the supercritical fluid processing. The elemental analysis and X-ray photoelectron spectroscopy revealed the amount and nature of N-doping in the graphene, respectively. The surface morphology and physical nature of the samples were analyzed using scanning and transmission electron microscopic analysis. The electrochemical performance of prepared electrode materials was evaluated using cyclic voltammetry, galvanostatic charge-discharge analysis and electrochemical impedance spectroscopy. The N-doped graphene prepared via supercritical fluid assisted processing exhibit enhanced capacitive behaviour with a maximum specific capacitance of 286 F g"−"1 at a current density of 0.5 A/g. The cycling studies showed 98% specific capacity retention with 100% coulombic efficiency over 1000 cycles at 5 A/g. The enhanced specific capacitance of N

  8. Silicon Based Direct Methanol Fuel Cells

    DEFF Research Database (Denmark)

    Larsen, Jackie Vincent

    The purpose of this project has been to investigate and fabricate small scale Micro Direct Methanol Fuel Cells (μDMFC). They are investigated as a possible alternative for Zinc-air batteries in small size consumer devices such as hearing aids. In such devices the conventional rechargeable batteries...... such as lithium-ion batteries have insufficiently low energy density. Methanol is a promising fuel for such devices due to the high energy density and ease of refueling compared to charging batteries, making μDMFC a suitable replacement energy source. In this Ph.D. dissertation, silicon micro fabrication...... techniques where utilized to build μDMFCs with the purpose of engineering the structures, both on the micro and nano scales in order to realize a high level of control over the membrane and catalyst components. The work presents four different monolithic fuel cell designs. The primary design is based...

  9. Self regulation in the methanol industry

    International Nuclear Information System (INIS)

    Hymas, R.; Wilkes, P.

    1995-01-01

    The methanol industry is not known for a high degree of self-regulation, as one can see from a glance at historic price volatility, and historic demand/supply curves. Industry enthusiasts spend considerable effort attempting to improve their understanding of the industry by analyzing the abundance of data produced within the industry about these topics, usually without resulting in any definitive correlations. Rational planning within the industry is hindered by these factors as well as the large number of new production facilities continuously being announced. Against this background however demand has significantly increased, supply has kept up with demand, methanol plants structured on a rational basis have continued to be built, and in spite of wildly fluctuating product prices all established members of the industry apparently flourish. Historic trends, new entrants, and industry achievements are discussed

  10. Notes on HTR applications in methanol production

    International Nuclear Information System (INIS)

    Santoso, B.; Barnert, H.

    1997-01-01

    Notes on the study of HTR applications are presented. The study in particular should be directed toward the most feasible applications of HTR for process heat generation. A prospective study is the conversion of CO 2 gas from Natuna to methanol or formic acid. Further studies needs to be deepened under the auspices of IAEA and countries that have similar interest. (author). 3 refs, 3 figs

  11. Reaction kinetics of cellulose hydrolysis in subcritical and supercritical water

    Science.gov (United States)

    Olanrewaju, Kazeem Bode

    The uncertainties in the continuous supply of fossil fuels from the crisis-ridden oil-rich region of the world is fast shifting focus on the need to utilize cellulosic biomass and develop more efficient technologies for its conversion to fuels and chemicals. One such technology is the rapid degradation of cellulose in supercritical water without the need for an enzyme or inorganic catalyst such as acid. This project focused on the study of reaction kinetics of cellulose hydrolysis in subcritical and supercritical water. Cellulose reactions at hydrothermal conditions can proceed via the homogeneous route involving dissolution and hydrolysis or the heterogeneous path of surface hydrolysis. The work is divided into three main parts. First, the detailed kinetic analysis of cellulose reactions in micro- and tubular reactors was conducted. Reaction kinetics models were applied, and kinetics parameters at both subcritical and supercritical conditions were evaluated. The second major task was the evaluation of yields of water soluble hydrolysates obtained from the hydrolysis of cellulose and starch in hydrothermal reactors. Lastly, changes in molecular weight distribution due to hydrothermolytic degradation of cellulose were investigated. These changes were also simulated based on different modes of scission, and the pattern generated from simulation was compared with the distribution pattern from experiments. For a better understanding of the reaction kinetics of cellulose in subcritical and supercritical water, a series of reactions was conducted in the microreactor. Hydrolysis of cellulose was performed at subcritical temperatures ranging from 270 to 340 °C (tau = 0.40--0.88 s). For the dissolution of cellulose, the reaction was conducted at supercritical temperatures ranging from 375 to 395 °C (tau = 0.27--0.44 s). The operating pressure for the reactions at both subcritical and supercritical conditions was 5000 psig. The results show that the rate-limiting step in

  12. Geological model of supercritical geothermal reservoir related to subduction system

    Science.gov (United States)

    Tsuchiya, Noriyoshi

    2017-04-01

    Following the Great East Japan Earthquake and the accident at the Fukushima Daiichi Nuclear power station on 3.11 (11th March) 2011, geothermal energy came to be considered one of the most promising sources of renewable energy for the future in Japan. The temperatures of geothermal fields operating in Japan range from 200 to 300 °C (average 250 °C), and the depths range from 1000 to 2000 m (average 1500 m). In conventional geothermal reservoirs, the mechanical behavior of the rocks is presumed to be brittle, and convection of the hydrothermal fluid through existing network is the main method of circulation in the reservoir. In order to minimize induced seismicity, a rock mass that is "beyond brittle" is one possible candidate, because the rock mechanics of "beyond brittle" material is one of plastic deformation rather than brittle failure. Supercritical geothermal resources could be evaluated in terms of present volcanic activities, thermal structure, dimension of hydrothermal circulation, properties of fracture system, depth of heat source, depth of brittle factures zone, dimension of geothermal reservoir. On the basis of the GIS, potential of supercritical geothermal resources could be characterized into the following four categories. 1. Promising: surface manifestation d shallow high temperature, 2 Probability: high geothermal gradient, 3 Possibility: Aseismic zone which indicates an existence of melt, 4 Potential : low velocity zone which indicates magma input. Base on geophysical data for geothermal reservoirs, we have propose adequate tectonic model of development of the supercritical geothermal reservoirs. To understand the geological model of a supercritical geothermal reservoir, granite-porphyry system, which had been formed in subduction zone, was investigated as a natural analog of the supercritical geothermal energy system. Quartz veins, hydrothermal breccia veins, and glassy veins are observed in a granitic body. The glassy veins formed at 500-550

  13. 10 MW Supercritical CO2 Turbine Test

    Energy Technology Data Exchange (ETDEWEB)

    Turchi, Craig

    2014-01-29

    The Supercritical CO2 Turbine Test project was to demonstrate the inherent efficiencies of a supercritical carbon dioxide (s-CO2) power turbine and associated turbomachinery under conditions and at a scale relevant to commercial concentrating solar power (CSP) projects, thereby accelerating the commercial deployment of this new power generation technology. The project involved eight partnering organizations: NREL, Sandia National Laboratories, Echogen Power Systems, Abengoa Solar, University of Wisconsin at Madison, Electric Power Research Institute, Barber-Nichols, and the CSP Program of the U.S. Department of Energy. The multi-year project planned to design, fabricate, and validate an s-CO2 power turbine of nominally 10 MWe that is capable of operation at up to 700°C and operates in a dry-cooled test loop. The project plan consisted of three phases: (1) system design and modeling, (2) fabrication, and (3) testing. The major accomplishments of Phase 1 included: Design of a multistage, axial-flow, s-CO2 power turbine; Design modifications to an existing turbocompressor to provide s-CO2 flow for the test system; Updated equipment and installation costs for the turbomachinery and associated support infrastructure; Development of simulation tools for the test loop itself and for more efficient cycle designs that are of greater commercial interest; Simulation of s-CO2 power cycle integration into molten-nitrate-salt CSP systems indicating a cost benefit of up to 8% in levelized cost of energy; Identification of recuperator cost as a key economic parameter; Corrosion data for multiple alloys at temperatures up to 650ºC in high-pressure CO2 and recommendations for materials-of-construction; and Revised test plan and preliminary operating conditions based on the ongoing tests of related equipment. Phase 1 established that the cost of the facility needed to test the power turbine at its full power and temperature would exceed the planned funding for Phases 2 and 3. Late

  14. A New 95 GHz Methanol Maser Catalog. I. Data

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Wenjin; Xu, Ye; Lu, Dengrong; Ju, Binggang; Li, Yingjie [Purple Mountain Observatory, Chinese Academy of Science, Nanjing 210008 (China); Chen, Xi [Center for Astrophysics, GuangZhou University, Guangzhou 510006 (China); Ellingsen, Simon P., E-mail: wjyang@pmo.ac.cn, E-mail: xuye@pmo.ac.cn, E-mail: chenxi@shao.ac.cn [School of Physical Sciences, University of Tasmania, Hobart, Tasmania (Australia)

    2017-08-01

    The Purple Mountain Observatory 13.7 m radio telescope has been used to search for 95 GHz (8{sub 0}–7{sub 1}A{sup +}) class I methanol masers toward 1020 Bolocam Galactic Plane Survey (BGPS) sources, leading to 213 detections. We have compared the line width of the methanol and HCO{sup +} thermal emission in all of the methanol detections, and on that basis, we find that 205 of the 213 detections are very likely to be masers. This corresponds to an overall detection rate of 95 GHz methanol masers toward our BGPS sample of 20%. Of the 205 detected masers, 144 (70%) are new discoveries. Combining our results with those of previous 95 GHz methanol maser searches, a total of 481 95 GHz methanol masers are now known. We have compiled a catalog listing the locations and properties of all known 95 GHz methanol masers.

  15. Study on fuel supplying method and methanol concentration sensor for the high efficient operation of methanol fuel cells. Methanol nenryo denchi no unten ni okeru nenryo kyokyu hoho no kento to methanol nodo sensor no kaihatsu

    Energy Technology Data Exchange (ETDEWEB)

    Tsukui, Tsutomu; Doi, Ryota; Yasukawa, Saburo; Kuroda, Osamu [Hirachi, Ltd., Tokyo, (Japan)

    1990-01-20

    A fuel supplying method was studied and demonstrated, essential to the high efficient operation of methanol fuel cells. Methanol and water were supplied independently from each tank to an anordic electrolyte tank in a circulating system, detecting a methanol concentration and liquid level of anordic electrolyte by each sensor, respectively. A methanol sensor was also developed to detect accurately the concentration based on electrochemical reaction under a constant voltage. A detection control circuit was insulated from a constant-voltage power supply to prevent external noises. The methanol sensor output was compensated for temperature, and a new level sensing method was adopted to send out a command comparing different responses to electrolyte shortage. As the methanol fuel cell was operated with this fuel supplying system, the stable characteristics of the cell were obtained within the variation of {plus minus} 0.1mol/l from the specified methanol concentration. 6 refs., 17 figs., 1 tab.

  16. Application of the GRI 1.2 Methane Oxidation Model to Methane and Methanol Oxidation in Supercritical Water

    National Research Council Canada - National Science Library

    Rice, Steven

    1997-01-01

    The Gas Research Institute (GRI) has been leading an effort over the past few years to consolidate recent developments in the elementary reaction modeling of the oxidation of methane for combustion applications into a single...

  17. Watching Nanoparticles Form: An In Situ (Small-/Wide-Angle X-ray Scattering/Total Scattering) Study of the Growth of Yttria-Stabilised Zirconia in Supercritical Fluids

    DEFF Research Database (Denmark)

    Tyrsted, Christoffer; Pauw, Brian; Jensen, Kirsten Marie Ørnsbjerg

    2012-01-01

    Understanding nanoparticle formation reactions requires multitechnique in situ characterisation, since no single characterisation technique provides adequate information. Here, the first combined small-angle X-ray scattering (SAXS)/wide-angle X-ray scattering (WAXS)/total-scattering study of nano...... of nanoparticle formation is presented. We report on the formation and growth of yttria-stabilised zirconia (YSZ) under the extreme conditions of supercritical methanol for particles with Y2O3 equivalent molar fractions of 0, 4, 8, 12 and 25%....

  18. Liquid methanol under a static electric field

    Energy Technology Data Exchange (ETDEWEB)

    Cassone, Giuseppe, E-mail: giuseppe.cassone@impmc.upmc.fr [Sorbonne Universités, UPMC Univ Paris 06, UMR 7590, IMPMC, F-75005 Paris (France); CNRS, UMR 7590, IMPMC, F-75005 Paris (France); Università degli Studi di Messina, Dipartimento di Fisica e di Scienze della Terra, Contrada Papardo, 98166 Messina (Italy); CNR-IPCF, Viale Ferdinando Stagno d’Alcontres 37, 98158 Messina (Italy); Giaquinta, Paolo V., E-mail: paolo.giaquinta@unime.it [Università degli Studi di Messina, Dipartimento di Fisica e di Scienze della Terra, Contrada Papardo, 98166 Messina (Italy); Saija, Franz, E-mail: saija@ipcf.cnr.it [CNR-IPCF, Viale Ferdinando Stagno d’Alcontres 37, 98158 Messina (Italy); Saitta, A. Marco, E-mail: marco.saitta@impmc.upmc.fr [Sorbonne Universités, UPMC Univ Paris 06, UMR 7590, IMPMC, F-75005 Paris (France); CNRS, UMR 7590, IMPMC, F-75005 Paris (France)

    2015-02-07

    We report on an ab initio molecular dynamics study of liquid methanol under the effect of a static electric field. We found that the hydrogen-bond structure of methanol is more robust and persistent for field intensities below the molecular dissociation threshold whose value (≈0.31 V/Å) turns out to be moderately larger than the corresponding estimate obtained for liquid water. A sustained ionic current, with ohmic current-voltage behavior, flows in this material for field intensities above 0.36 V/Å, as is also the case of water, but the resulting ionic conductivity (≈0.40 S cm{sup −1}) is at least one order of magnitude lower than that of water, a circumstance that evidences a lower efficiency of proton transfer processes. We surmise that this study may be relevant for the understanding of the properties and functioning of technological materials which exploit ionic conduction, such as direct-methanol fuel cells and Nafion membranes.

  19. Lightweight Stacks of Direct Methanol Fuel Cells

    Science.gov (United States)

    Narayanan, Sekharipuram; Valdez, Thomas

    2004-01-01

    An improved design concept for direct methanol fuel cells makes it possible to construct fuel-cell stacks that can weigh as little as one-third as much as do conventional bipolar fuel-cell stacks of equal power. The structural-support components of the improved cells and stacks can be made of relatively inexpensive plastics. Moreover, in comparison with conventional bipolar fuel-cell stacks, the improved fuel-cell stacks can be assembled, disassembled, and diagnosed for malfunctions more easily. These improvements are expected to bring portable direct methanol fuel cells and stacks closer to commercialization. In a conventional bipolar fuel-cell stack, the cells are interspersed with bipolar plates (also called biplates), which are structural components that serve to interconnect the cells and distribute the reactants (methanol and air). The cells and biplates are sandwiched between metal end plates. Usually, the stack is held together under pressure by tie rods that clamp the end plates. The bipolar stack configuration offers the advantage of very low internal electrical resistance. However, when the power output of a stack is only a few watts, the very low internal resistance of a bipolar stack is not absolutely necessary for keeping the internal power loss acceptably low.

  20. Experimental study of elliptical jet from sub to supercritical conditions

    Energy Technology Data Exchange (ETDEWEB)

    Muthukumaran, C. K.; Vaidyanathan, Aravind, E-mail: aravind7@iist.ac.in [Department of Aerospace Engineering, Indian Institute of Space Science and Technology, Trivandrum, Kerala 695547 (India)

    2014-04-15

    The jet mixing at supercritical conditions involves fluid dynamics as well as thermodynamic phenomena. All the jet mixing studies at critical conditions to the present date have focused only on axisymmetric jets. When the liquid jet is injected into supercritical environment, the thermodynamic transition could be well understood by considering one of the important fluid properties such as surface tension since it decides the existence of distinct boundary between the liquid and gaseous phase. It is well known that an elliptical liquid jet undergoes axis-switching phenomena under atmospheric conditions due to the presence of surface tension. The experimental investigations were carried out with low speed elliptical jet under supercritical condition. Investigation of the binary component system with fluoroketone jet and N{sub 2} gas as environment shows that the surface tension force dominates for a large downstream distance, indicating delayed thermodynamic transition. The increase in pressure to critical state at supercritical temperature is found to expedite the thermodynamic transition. The ligament like structures has been observed rather than droplets for supercritical pressures. However, for the single component system with fluoroketone jet and fluoroketone environment shows that the jet disintegrates into droplets as it is subjected to the chamber conditions even for the subcritical pressures and no axis switching phenomenon is observed. For a single component system, as the pressure is increased to critical state, the liquid jet exhibits gas-gas like mixing behavior and that too without exhibiting axis-switching behavior.